Thin film manufacturing method

Abstract

The present invention relates to a method for producing a thin film, comprising: a step (i) for adsorbing a growth inhibitor for forming a thin film represented by chemical formula 1 on the surface of a substrate; and (ii) adsorbing the Ti-based thin film precursor on the surface of the substrate on which the growth inhibitor for thin film formation has been adsorbed. According to the invention, by inhibiting side reaction, reducing the growth rate of the thin film and removing process byproducts in the thin film, even if the thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film are greatly improved. The chemical formula 1 is AnBmXo, in the chemical formula 1, A is carbon or silicon, B is hydrogen or alkyl with the carbon atom number being 1-3, X is halogen, n is an integer ranging from 1 to 15, o is an integer larger than 1, and m is 0-2n + 1.

Description

[0001] This application is a divisional application of the invention patent application with the application date of February 24, 2020, application number 202010111582.6, and invention name “Thin Film Manufacturing Method”. Technical Field

[0002] The present invention relates to a thin film manufacturing method, and more particularly to a thin film manufacturing method that significantly improves step coverage and thickness uniformity of a thin film by inhibiting side reactions, appropriately reducing a thin film growth rate, and removing process byproducts within the thin film to prevent corrosion and degradation, even when the thin film is formed on a substrate with a complex structure. Background Art

[0003] The integration level of storage and non-storage semiconductor devices is increasing day by day. As their structures become more and more complex, the importance of step coverage is increasing when depositing multiple thin films on a substrate.

[0004] The semiconductor thin film is formed of metal nitride, metal oxide, metal silicide, etc. The metal nitride thin film includes titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (ZrN) and other thin films, which are generally used as diffusion barriers between the silicon layer of the doped semiconductor and aluminum (Al), copper (Cu) and other materials used as interlayer wiring. However, when a tungsten (W) thin film is deposited on a substrate, it is used as an adhesion layer.

[0005] In order to obtain excellent and uniform physical properties of the thin film deposited on the substrate, the formed thin film needs to have excellent step coverage. Therefore, compared with the chemical vapor deposition (CVD) process that mainly uses gas phase reactions, the atomic layer deposition (ALD) process that uses surface reactions is more often used, but there are still problems in achieving 100% step coverage.

[0006] In addition, titanium tetrachloride (TiCl4) is used to deposit titanium nitride (TiN), which is a representative metal nitride. At this time, process byproducts such as chlorides will remain in the manufactured film, thereby inducing corrosion of metals such as aluminum and causing degradation of film quality due to the generation of non-volatile byproducts.

[0007] Therefore, it is necessary to develop a method for manufacturing a thin film that can form a thin film with a complex structure without corroding the interlayer wiring material.

[0008] Prior Art Literature

[0009] Patent Literature

[0010] (Patent Document 0001) Korean Patent Publication No. 2006-0037241 Summary of the invention

[0011] Technical issues

[0012] In order to solve the problems of the prior art as described above, the object of the present invention is to provide a thin film manufacturing method, which prevents corrosion and degradation by inhibiting side reactions, appropriately reducing the thin film growth rate, and removing process by-products in the thin film. Even when the thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film are greatly improved.

[0013] The above-mentioned object and other objects of the present invention can be achieved by the present invention described below.

[0014] Technical Solution

[0015] In order to achieve the above object, the present invention provides a thin film manufacturing method, which comprises: step (i), allowing a thin film formation growth inhibitor represented by chemical formula 1 to be adsorbed on a substrate surface; and step (ii), allowing a Ti-based thin film precursor to be adsorbed on the substrate surface adsorbed with the thin film formation growth inhibitor,

[0016] Chemical formula 1:

[0017] A n B m X o

[0018] Wherein, 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 1, and m is 0 to 2n+1.

[0019] In addition, the present invention provides a thin film manufacturing device, which includes: an ALD (atomic layer deposition) chamber; a first vaporizer, which vaporizes a growth inhibitor for thin film formation; a first transfer unit, which transfers the vaporized growth inhibitor for thin film formation into the ALD chamber; a second vaporizer, which vaporizes a Ti-based thin film precursor; and a second transfer unit, which transfers the vaporized Ti-based thin film precursor into the ALD chamber.

[0020] Beneficial Effects

[0021] The present invention provides a thin film manufacturing method, which appropriately reduces the film growth rate by inhibiting side reactions and reducing the deposition rate, and prevents corrosion and degradation by removing process byproducts in the thin film. Even when the thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film are greatly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a process diagram for explaining a conventional ALD process.

[0023] Figure 2 It is a process diagram for explaining an ALD process according to an embodiment of the present invention.

[0024] Figure 3 It is a graph showing the change in film thickness of Example 7 (SP-TiCl4) of the present invention and Comparative Example 1 (TiCl4) as the ALD cycle increases.

[0025] Figure 4 It is a graph showing the change in deposition rate of Examples 7-1 to 7-3 of the present invention and Comparative Example 1 depending on the feeding time of a growth inhibitor (SP) for thin film formation per ALD cycle.

[0026] Figure 5 These are transmission electron microscope (TEM) images of the TiN thin films deposited in Example 1 (SP-TiCl4) of the present invention and Comparative Example 1 (TiCl4). DETAILED DESCRIPTION

[0027] Hereinafter, the thin film production method of the present invention will be described in detail.

[0028] The inventors of the present invention have confirmed that when a halogenated compound with a specified structure is first adsorbed on the surface of a substrate as a growth inhibitor before depositing a Ti-based thin film precursor onto the surface of a substrate loaded inside an ALD chamber, the growth rate of the thin film formed after deposition is reduced, and the halide remaining as a process by-product is greatly reduced, thereby greatly improving the step coverage, etc. Based on this, further research was conducted and the present invention was completed.

[0029] The thin film manufacturing method of the present invention comprises: step (i), allowing the growth inhibitor for thin film formation represented by chemical formula 1 to be adsorbed on the surface of a substrate; and step (ii), allowing a Ti-based thin film precursor to be adsorbed on the surface of the substrate adsorbed with the growth inhibitor for thin film formation,

[0030] Chemical formula 1:

[0031] A n B m Xo

[0032] Wherein, 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 of 1 to 15, o is an integer greater than 1, and m is 0 to 2n+1. In this case, when a thin film is formed, the film growth rate is reduced by suppressing side reactions, and corrosion and degradation are reduced by removing process byproducts in the thin film. Even when a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film are greatly improved.

[0033] In the step (i) of adsorbing the growth inhibitor for thin film formation on the surface of the substrate, the feeding time (Feeding Time) of the growth inhibitor for thin film formation on the surface of the substrate is preferably 1 to 10 seconds, more preferably 1 to 5 seconds, more preferably 2 to 5 seconds, and further preferably 2 to 4 seconds. Within this range, the thin film growth rate is low, and the step coverage and economy are excellent.

[0034] In the present invention, the feeding 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, a chamber volume of 18 L and a flow rate of 1 to 2 mg / s.

[0035] As a preferred example, the step (i) of allowing the growth inhibitor for thin film formation to be adsorbed on the surface of the substrate may include the step of injecting the growth inhibitor for thin film formation into the ALD chamber and allowing it to be adsorbed on the surface of the loaded substrate. In this case, the thin film growth rate is reduced and the process by-products in the thin film are removed by suppressing side reactions and reducing the deposition rate.

[0036] In the step (i) of adsorbing the growth inhibitor for thin film formation on the surface of the substrate, it is preferred to use a purge gas to purge the residual growth inhibitor for thin film formation that has not been adsorbed on the surface of the substrate. At this time, the advantage is that when the thin film is formed, the film growth rate is reduced by inhibiting side reactions, and corrosion and degradation are reduced by removing process by-products in the thin film. Even when the thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film are greatly improved.

[0037] Furthermore, in the step (ii) of adsorbing the Ti-based thin film precursor, it is preferred that the residual Ti-based thin film precursor that has not been adsorbed is purged using a purge gas.

[0038] The thin film manufacturing method preferably includes the following steps: after the Ti-based thin film precursor is adsorbed on the surface of the substrate, a reaction gas is supplied, and a reaction byproduct of the Ti-based thin film precursor and the reaction gas is purged using a purge gas.

[0039] As a preferred embodiment, the thin film manufacturing method may include the following steps: a) vaporizing the growth inhibitor for thin film formation and adsorbing it onto the surface of the substrate loaded in the ALD chamber; b) purging the inside of the ALD chamber for the first time with a purge gas; c) vaporizing the Ti-based thin film precursor and adsorbing it onto the surface of the substrate loaded in the ALD chamber; d) purging the inside of the ALD chamber for the second time with a purge gas; e) supplying a reaction gas to the inside of the ALD chamber; and f) purging the inside of the ALD chamber for the third time with a purge gas. In this case, the advantage is that the film growth rate is appropriately reduced, and even if the deposition temperature is increased when the film is formed, the generated process byproducts are effectively removed, thereby reducing the resistivity of the film and greatly improving the step coverage.

[0040] The thin film formation growth inhibitor and the Ti-based thin film precursor may be preferably transferred into the ALD chamber, that is, onto the substrate surface, by VFC, DLI or LDS, and more preferably transferred into the ALD chamber by LDS.

[0041] The ratio of the amount (mg / cycle) of the growth inhibitor for thin film formation to the amount of the precursor compound input into the ALD chamber can be preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, more preferably 1:2 to 1:12, and further preferably 1:2.5 to 1:10. Within this range, the reduction rate of the thin film growth rate per cycle (GPC) is high and the effect of reducing process by-products is good.

[0042] When the Ti-based thin film precursor is a Ti-based thin film precursor commonly used in an ALD (atomic layer deposition) method, there is no particular limitation. As a preferred embodiment, it may be titanium tetrahalide.

[0043] The titanium tetrahalide may preferably be at least one selected from TiF4, TiCl4, TiBr4 and TiI4, for example, TiCl4 is preferred in terms of economy, but is not limited thereto.

[0044] However, since the titanium tetrahalide has excellent thermal stability, does not decompose at room temperature and exists in a liquid state, it can be well used as a thin film precursor for depositing a thin film by the ALD (atomic layer deposition) method.

[0045] As an example, the Ti-based thin film precursor may be mixed with a non-polar solvent and introduced into the chamber. In this case, the viscosity and vapor pressure of the Ti-based thin film precursor may be easily adjusted.

[0046] The non-polar solvent may preferably be at least one selected from alkanes and cycloalkanes. In this case, the non-polar solvent has the advantage of containing an organic solvent with low reactivity and solubility and easy moisture management, and even if the deposition temperature is increased during film formation, the step coverage can be improved.

[0047] As a more preferred example, the non-polar solvent may include C1-C10 alkane or C3-C10 cycloalkane, preferably C3-C10 cycloalkane. In this case, the reactivity and solubility are low and moisture management is easy.

[0048] In the present invention, C1, C3, etc. represent the number of carbon atoms.

[0049] The cycloalkane may preferably be a C3-C10 monocycloalkane. Among the monocycloalkane, cyclopentane is liquid at room temperature and has the highest vapor pressure, and is preferred in the vapor deposition process, but is not limited thereto.

[0050] As an example, the solubility of the non-polar solvent in water (25°C) is less than 200 mg / L, preferably 50 to 200 mg / L, and more preferably 135 to 175 mg / L. Within this range, the reactivity to the Ti-based thin film precursor is low and moisture management is easy.

[0051] In the present invention, when the solubility is based on a commonly used measurement method or benchmark in the technical field to which the present invention belongs, there is no particular limitation. As an embodiment, a saturated solution can be measured by HPLC.

[0052] Based on the total weight of the Ti-based thin film precursor and the non-polar solvent, the content of the non-polar solvent may be preferably 5-95% by weight, more preferably 10-90% by weight, even more preferably 40-90% by weight, and most preferably 70-90% by weight.

[0053] If the content of the non-polar solvent is greater than the above upper limit, impurities will be generated, resulting in an increase in the resistance and impurity values ​​in the film. When the content of the organic solvent is less than the above lower limit, the effect of increasing the step coverage and reducing impurities such as chloride (Cl) ions caused by adding the solvent is not good.

[0054] As an example, in the thin film manufacturing method, the thin film growth rate per cycle calculated by Mathematical Formula 1 ( ) is less than -5%, preferably less than -10%, more preferably less than -20%, even more preferably less than -30%, further preferably less than -40%, and most preferably less than -45%. Within this range, the step coverage and film thickness uniformity are excellent.

[0055] Mathematical formula 1:

[0056] Reduction rate of thin film growth rate per cycle (%) = [(thin film growth rate per cycle when using a thin film formation growth inhibitor - thin film growth rate per cycle when not using a thin film formation growth inhibitor) / thin film growth rate per cycle when not using a thin film formation growth inhibitor] × 100

[0057] In the thin film manufacturing method, the residual halogen intensity (c / s) in the thin film formed after 200 cycles based on SIMS measurement can be preferably less than 10,000, more preferably less than 8,000, more preferably less than 7,000, and further preferably less than 6,000. Within this range, the effect of preventing corrosion and degradation is excellent.

[0058] In the present invention, the purge 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 which the film growth rate per cycle is reduced to a preferred range and process byproducts are reduced.

[0059] The ALD (atomic layer deposition) process is very advantageous in the production of integrated circuits (ICs) that require a high aspect ratio, especially because it is based on a self-limiting thin film growth mechanism and has the advantages of excellent step conformality, uniform coverage, and precise thickness control.

[0060] As an example, the thin film manufacturing method can be implemented at a deposition 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 further preferably in the range of 400 to 500°C. Within this range, the ALD process characteristics can be achieved and a thin film with excellent film quality can be grown.

[0061] As an example, the thin film manufacturing method can be implemented at a steam pressure in the range of 0.1 to 10 Torr, preferably in the range of 0.5 to 5 Torr, and most preferably in the range of 1 to 3 Torr. Within this range, a thin film with uniform thickness can be obtained.

[0062] In the present invention, the deposition temperature and the deposition pressure may be measured by the temperature and pressure formed in the deposition chamber, or may be measured by the temperature and pressure applied to the substrate in the deposition chamber.

[0063] The thin film manufacturing method may preferably include: a step of raising the temperature in the chamber to the deposition temperature before introducing the growth inhibitor for thin film formation into the chamber; and / or a step of injecting an inert gas into the chamber for purging before introducing the growth inhibitor for thin film formation into the chamber.

[0064] In addition, the present invention relates to a thin film manufacturing device, which can implement the thin film manufacturing method, including: an ALD chamber; a first vaporizer, which vaporizes a growth inhibitor for thin film formation; a first transfer unit, which transfers the vaporized growth inhibitor for thin film formation into the ALD chamber; a second vaporizer, which vaporizes a Ti-based thin film precursor; and a second transfer unit, which transfers the vaporized Ti-based thin film precursor into the ALD chamber. There is no particular limitation when the vaporizer and the transfer unit are commonly used in the technical field to which the present invention belongs.

[0065] As a specific example, the thin film production method will be described.

[0066] First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of performing atomic layer deposition.

[0067] The substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0068] The substrate may further have a conductive layer or an insulating layer formed on an upper portion thereof.

[0069] In order to deposit a thin film on the substrate in the deposition chamber, the growth inhibitor for thin film formation and the Ti-based thin film precursor or a mixture of the Ti-based thin film precursor and a non-polar solvent are prepared.

[0070] Then, the prepared thin film forming inhibitor is injected into the vaporizer, converted into a vapor phase, and transferred to the deposition chamber, where it is adsorbed on the substrate, and the unadsorbed thin film forming inhibitor is purged.

[0071] Then, after the prepared Ti-based thin film precursor or a mixture of the Ti-based thin film precursor and a non-polar solvent is injected into the vaporizer, it is converted into a vapor phase and transferred to the deposition chamber, thereby being adsorbed on the substrate and purging the unadsorbed thin film forming composition.

[0072] As an example, in the present invention, the method for transferring the inhibitor for thin film formation and the Ti-based thin film precursor to the deposition chamber can adopt a method of transferring the volatilized gas (Vapor Flow Control; VFC) using a gas phase flow control (Mass Flow Controller; MFC) method or a method of transferring the liquid (Liquid Delivery System; LDS) using a liquid phase flow control (Liquid Mass Flow Controller; LMFC) method, and the LDS method is preferably used.

[0073] At this time, as a carrier gas or dilution gas for moving thin film forming inhibitors and Ti-based thin film precursors to the substrate, one or a mixed gas selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but it is not limited to this.

[0074] As an example, in the present invention, the purge gas may be an inert gas, and preferably the carrier gas or the diluent gas.

[0075] Then, a reaction gas is supplied. When the reaction gas is a reaction gas commonly used in the technical field to which the present invention belongs, there is no particular limitation, and it may preferably include a reducing agent, a nitriding 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, the nitriding agent forms a metal nitride thin film, and the oxidizing agent forms a metal oxide thin film.

[0076] Preferably, the reducing agent may be ammonia (NH3) or hydrogen (H2), the nitriding agent may be nitrogen (N2), and the oxidizing agent may be one or more selected from H2O, H2O2, O2, O3 and N2O.

[0077] Then, the residual reaction gas that has not participated in the reaction is purged with an inert gas. In this way, not only the excess reaction gas but also the generated by-products can be removed at the same time.

[0078] As described above, a unit cycle includes the steps of adsorbing a thin film forming inhibitor on a substrate, purging unadsorbed thin film forming inhibitors, adsorbing a Ti-based thin film precursor on a substrate, purging unadsorbed thin film forming compositions, supplying reaction gases, and purging residual reaction gases, and the unit cycle can be repeated to form a thin film having a desired thickness.

[0079] As an example, the unit cycle may be performed 100 to 1000 times, preferably 100 to 500 times, and more preferably 150 to 300 times. Within this range, the desired film characteristics are well expressed.

[0080] Figure 1 This is a process diagram for explaining the existing ALD process. Figure 2 1 is a process diagram for explaining an ALD process according to an embodiment of the present invention. Figure 1 When the thin film formation growth inhibitor 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 byproducts such as HCl will remain in the thin film (TiN) formed by the reaction with the reaction gas (NH3), thereby reducing the performance of the substrate due to corrosion and degradation. Figure 2 As shown, when the thin film formation growth inhibitor (Inhibitor; TSI) of the present invention is adsorbed before the Ti-based thin film precursor (TiCl4) is adsorbed to perform substrate surface protection (Surface Protection; SP), process byproducts such as HCl generated by reaction with the reaction gas (NH3) during the formation of the thin film (TiN) can be removed together with the thin film formation growth inhibitor, thereby preventing corrosion and degradation of the substrate, and then appropriately reducing the thin film growth rate per cycle, and improving the step coverage and uniformity of the film thickness.

[0081] The growth inhibitor for thin film formation of the present invention is preferably a compound represented by Chemical Formula 1,

[0082] Chemical formula 1:

[0083] A n B m X o

[0084] Wherein, 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 of 1 to 15, o is an integer greater than 1, and m is 0 to 2n+1. In this case, when a thin film is formed, the film growth rate is reduced by suppressing side reactions, and corrosion and degradation are reduced by removing process byproducts in the thin film. Even when a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film are greatly improved.

[0085] The B is preferably hydrogen or methyl, and the n is preferably an integer from 2 to 15, more preferably an integer from 2 to 10, more preferably an integer from 2 to 6, and further preferably an integer from 4 to 6. Within this range, the process by-product removal effect is good and the step coverage is excellent.

[0086] As an example, in the chemical formula 1, X may be one or more selected from F, Cl, Br and I, and may preferably be Cl (chlorine). In this case, side reactions are suppressed and process by-products are effectively removed.

[0087] In the chemical formula 1, the o may preferably be 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 deposition rate is effectively reduced, and therefore, it is more effective in improving the step coverage.

[0088] The m is preferably 1 to 2n+1, and more preferably 3 to 2n+1. Within this range, the process by-product removal effect is good and the step coverage is excellent.

[0089] The compound represented by the chemical formula 1 may preferably be a branched compound, a cyclic compound or an aromatic compound. As a specific example, it is one or more selected from 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, chlorocyclopentane, 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. At this time, the advantage is that the process by-product removal effect is good and the step coverage is excellent.

[0090] The compound represented by the chemical formula 1 is preferably used in an atomic layer deposition (ALD) process. At this time, it has the advantage that it does not hinder the adsorption of Ti-based thin film precursors, and at the same time, as a growth inhibitor, it effectively protects the surface of the substrate (Surface Protection; SP) and effectively removes process byproducts.

[0091] The compound represented by the chemical formula 1 may preferably be liquid at room temperature (22° C.) and have a density of 0.8 to 1.5 g / cm 3 , vapor pressure (20°C) is 1 to 300 mmHg, and solubility in water (25°C) is below 200 mg / L. Within this range, the step coverage and film thickness uniformity are excellent.

[0092] More preferably, the compound represented by the chemical formula 1 may have a density of 0.85 to 1.3 g / cm 3 , vapor pressure (20°C) is 1 to 260 mmHg, and solubility in water (25°C) is below 160 mg / L. Within this range, the step coverage and film thickness uniformity are excellent.

[0093] The semiconductor substrate of the present invention is manufactured by the thin film manufacturing method of the present invention. In this case, the thin film growth rate is appropriately reduced by suppressing side reactions, and corrosion and degradation are prevented by removing process byproducts in the thin film, and the step coverage and thickness uniformity of the thin film are excellent.

[0094] Preferably, the thickness of the film manufactured above is less than 20nm, the resistivity value is 0.1 to 400μΩ·cm, the halogen content is less than 10,000ppm, and the step coverage is more than 90%. Within this range, it performs excellently as an anti-diffusion film and reduces corrosion of metal wiring materials, but is not limited to this.

[0095] As an example, the thickness of the film may be 5 to 20 nm, preferably 10 to 20 nm, more preferably 15 to 18.5 nm, and even more preferably 17 to 18.5 nm. Within this range, the film properties are excellent.

[0096] As an example, the resistivity value of the film can be 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, further preferably 330 to 380 μΩ·cm, and most preferably 340 to 370 μΩ·cm. Within this range, the film properties are excellent.

[0097] The halogen content of the film may more preferably be 9,000 ppm or less or 1 to 9,000 ppm, further preferably 8,500 ppm or less or 100 to 8,500 ppm, further preferably 8,200 ppm or less or 1,000 to 8,200 ppm, within which range the film properties are excellent and corrosion of metal wiring materials is reduced.

[0098] As an example, the step coverage of the film is above 80%, preferably above 90%, and more preferably above 92%. Within this range, even a thin film with a complex structure can be easily deposited on the substrate, and thus can be applied to a new generation of semiconductor devices.

[0099] As an example, the thin film manufactured as described above may be a TiN thin film or a TiO2 thin film.

[0100] Below, in order to help understand the present invention, preferred embodiments and drawings are proposed. However, it is clear to those skilled in the art that the following embodiments and drawings are only used to illustrate the present invention, and various changes and modifications can be made within the scope of the scope of the present invention and technical ideas, and such deformation and modification undoubtedly fall within the scope of the attached claims.

[0101] [Example]

[0102] Examples 1 to 7

[0103] Prepare the thin film formation growth inhibitor and TiCl4 as a Ti-based thin film precursor described in Table 1 below. The prepared thin film formation growth inhibitor is loaded into a tank and supplied to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using a LMFC (Liquid Mass Flow Controller) at room temperature. After the thin film formation growth inhibitor vaporized into a vapor phase in the vaporizer is introduced into a deposition chamber loaded with a substrate for 3 seconds, argon is supplied at 3000 sccm for 6 seconds to purge with argon. At this time, the pressure in the reaction chamber is controlled to 1.3 Torr. Then, the prepared TiCl4 is loaded into another tank and supplied to another vaporizer heated to 150°C at a flow rate of 0.05 g / min using a LMFC (Liquid Mass Flow Controller) at room temperature. After TiCl4 vaporized in the vaporizer into a vapor phase is introduced into the deposition chamber for 3 seconds, argon gas is supplied at 3000 sccm for 6 seconds to purge with argon gas. At this time, the pressure in the reaction chamber is controlled to be 1.3 Torr. Then, ammonia gas is introduced into the reaction chamber as a reaction gas for 5 seconds, and then argon gas is purged for 10 seconds. At this time, the substrate on which the metal film is to be formed is heated to 460°C. This process is repeated 200 times to form a TiN film as a self-limiting atomic layer.

[0104] Table 1

[0105] category Growth inhibitors for thin film formation Example 1 2-chloro-2-methylbutane Example 2 n-butyl chloride Example 3 Trimethylchlorosilane Example 4 2-chloropropane Example 5 1,2,3-trichloropropane Example 6 2-methyl-1-pentane Example 7 1,2-dichlorobenzene

[0106] Comparative Example 1

[0107] A TiN thin film was formed on the substrate in the same manner as in Example 1, except that the thin film formation growth inhibitor of Example 1 was not used and thus the step of purging the unadsorbed thin film formation growth inhibitor was omitted.

[0108] Comparative Examples 2 and 3

[0109] A TiN thin film was formed on a substrate in the same manner as in Example 1, except that pentane or cyclopentane was used instead of the growth inhibitor for thin film formation in Example 1 described in Table 1.

[0110] Experimental example

[0111] 1) Deposition evaluation

[0112] Referring to Table 2 below, Example 1 in which 2-chloro-2-methylbutane was used 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 / Cycle, the deposition rate was reduced by more than 55.5% compared with Comparative Example 1. It can be confirmed that the remaining Examples 2 to 7 also have deposition rates of values ​​similar to those of Example 1. In addition, it can be confirmed that Comparative Examples 2 and 3, which do not use the growth inhibitor for thin film formation of the present invention but use pentane or cyclopentane, also have deposition rates of values ​​similar to those of Comparative Example 1. At this time, the reduction in deposition rate indicates that the CVD deposition characteristics are changed to the ALD deposition characteristics, and can therefore be used as an indicator for improving the step coverage characteristics.

[0113] Table 2

[0114]

[0115] In addition, as shown in Table 3 below, it can be confirmed that the deposition rate continues to decrease as the injection amount of 2-chloro-2-methylbutane as a growth inhibitor for thin film formation increases. Example 1-1 was carried out in the same manner as Example 1 except for the injection amount of the growth inhibitor for thin film formation per cycle.

[0116] Table 3

[0117]

[0118] 2) Impurity reduction characteristics

[0119] In order to compare the impurity reduction characteristics, that is, the process by-product reduction characteristics, of the TiN films deposited in Example 1 and Comparative Example 1, SIMS analysis was performed, and the results are shown in Table 4 below.

[0120] Table 4

[0121] category Example 1 Comparative Example 1 Injection amount per ALD cycle (mg / cycle) 1.6 0 Cl intensity (c / s) 5907.05 17270.25

[0122] As shown in Table 4, it can be confirmed that the Cl intensity of Example 1 using the growth inhibitor for thin film formation of the present invention is reduced to 1 / 3 of that of Comparative Example 1 not using the growth inhibitor for thin film formation of the present invention.

[0123] in addition, Figure 3 This is a graph showing the change in film thickness of Example 7 (SP-TiCl4) of the present invention and Comparative Example 1 (TiCl4) as the ALD cycle increases. It can be confirmed that the thickness of the film of Example 7 is significantly thinned.

[0124] in addition, Figure 4: is a graph showing the deposition rate of Examples 7-1 to 7-3 of the present invention and Comparative Example 1 as a function of the feeding time of the growth inhibitor (SP) for thin film formation per ALD cycle. It can be determined that when the thin film formation inhibitor of the present invention is not used as in Comparative Example 1, the deposition rate per cycle is approximately In the case of Examples 7-1, 7-2, and 7-3, in which the inhibitor for thin film formation of the present invention was added for 0.7 seconds, 1 second, and 2 seconds, respectively, the deposition rate was significantly reduced to Except for the amount of the growth inhibitor for thin film formation used in Example 7, Examples 7-1, 7-2, and 7-3 were carried out in the same manner.

[0125] 3) Step coverage characteristics

[0126] The step coverage of the TiN films deposited in Example 1 and Comparative Example 1 was determined using TEM. The results are shown in Tables 5 and Figure 5 .

[0127] Table 5

[0128] category Example 1 Comparative Example 1 Ladder coverage rate (%) 92％ 78％

[0129] As shown in Table 5, it can be confirmed that Example 1 using the growth inhibitor for thin film formation of the present invention has significantly higher step coverage than Comparative Example 1 not using the growth inhibitor for thin film formation of the present invention.

[0130] In addition, refer to Figure 5 From the TEM images, it can be determined that the thickness uniformity of the top and bottom of the TiN film deposited in Example 1 (SP-TiCl4) is better than that of the TiN film deposited in Comparative Example 1 (TiCl4), and the step coverage is better.

Claims

1. A method for producing a thin film, characterized in that: include: Step (i), allowing a growth inhibitor for thin film formation represented by Chemical Formula 1 to be adsorbed on the surface of a substrate; as well as Step (ii), adsorbing a Ti-based thin film precursor onto the surface of a substrate adsorbed with a growth inhibitor for thin film formation, Chemical formula 1: A n B m X o Wherein, 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 1, and m is 0 to 2n+1.

2. The thin film manufacturing method according to claim 1, characterized in that: In the step (i) of allowing the growth inhibitor for thin film formation to be adsorbed on the surface of the substrate, the growth inhibitor for thin film formation is supplied to the surface of the substrate for a period of 1 to 10 seconds.

3. The thin film manufacturing method according to claim 1, characterized in that: In the step (i) of allowing the growth inhibitor for thin film formation to be adsorbed on the surface of the substrate, the growth inhibitor for thin film formation is injected into an ALD (atomic layer deposition) chamber and adsorbed on the surface of the loaded substrate.

4. The thin film manufacturing method according to claim 1, characterized in that: In the step (i) of allowing the thin film formation growth inhibitor to be adsorbed on the substrate surface, the residual thin film formation growth inhibitor that is not adsorbed on the substrate surface is purged using a purge gas.

5. The thin film manufacturing method according to claim 1, characterized in that: In the step (ii) of adsorbing the Ti-based thin film precursor, the residual Ti-based thin film precursor that has not been adsorbed is purged using a purge gas.

6. The thin film manufacturing method according to claim 1, characterized in that: The steps include: After the Ti-based thin film precursor is adsorbed on the surface of the substrate, a reaction gas is supplied; and The purge gas is used to purge the reaction byproducts of the Ti-based thin film precursor and the reaction gas.

7. The thin film manufacturing method according to claim 6, characterized in that: The reaction gas is a reducing agent, a nitriding agent or an oxidizing agent.

8. The thin film manufacturing method according to claim 1, characterized in that: The growth inhibitor for thin film formation and the Ti-based thin film precursor are transferred to the substrate surface by a VFC method, a DLI method or an LDS method.

9. The thin film manufacturing method according to claim 1, characterized in that: The ratio of the amount (mg / cycle) of the growth inhibitor for thin film formation to the amount (mg / cycle) of the Ti-based thin film precursor added to the substrate surface is 1:1.5 to 1:

20.

10. The thin film manufacturing method according to claim 1, characterized in that: In the chemical formula 1, X is chlorine (Cl).

11. The thin film manufacturing method according to claim 1, characterized in that: In the chemical formula 1, o is an integer of 1 to 5.

12. The thin film manufacturing method according to claim 1, characterized in that: The compound represented by the chemical formula 1 is a branched compound, a cyclic compound or an aromatic compound.

13. The thin film manufacturing method according to claim 1, characterized in that: The compound represented by the chemical formula 1 is liquid at room temperature 22°C and has a density of 0.8 to 1.5 g / cm 3 The vapor pressure at 20°C is 1 to 300 mmHg, and the solubility in water at 25°C is less than 200 mg / L.

14. The thin film manufacturing method according to claim 1, characterized in that: The film growth rate per cycle is calculated by Equation 1 The reduction rate is less than -5%, Mathematical formula 1: Reduction rate of film growth rate per cycle (%) = [(film growth rate per cycle when using growth inhibitor for film formation - film growth rate per cycle when not using growth inhibitor for film formation) / film growth rate per cycle when not using growth inhibitor for film formation] × 100.

15. The thin film manufacturing method according to claim 1, characterized in that: The residual halogen intensity (c / s) in the film formed after 200 cycles measured by SIMS was 10,000 or less.

16. A thin film manufacturing device, characterized in that: include: ALD (atomic layer deposition) chamber; a first vaporizer for vaporizing a growth inhibitor for thin film formation; A first transfer unit transfers the vaporized growth inhibitor for thin film formation into the ALD chamber; a second vaporizer for vaporizing a Ti-based thin film precursor; as well as The second transfer unit transfers the vaporized Ti-based thin film precursor into the ALD chamber.

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