Method and apparatus for manufacturing thin film

Abstract

To provide a method for manufacturing a thin film, capable of greatly improving step coverability and thin film thickness uniformity even when forming a thin film on a substrate having a complicated structure by controlling a side reaction to reduce a thin film growth rate and removing a process by-product in the thin film.SOLUTION: A method for manufacturing a thin film comprises the steps of: i) adsorbing a growth inhibitor for thin film formation represented by chemical formula (1) on a substrate surface; and ii) adsorbing a Ti-based thin film precursor on the substrate surface having the adsorbed growth inhibitor. AnBmXo (1) (where, A is carbon or silicon; B is hydrogen or 1-3C alkyl; X is halogen; n is any integer of 1-15; o is an integer of one or more; and m is 0 to 2n+1.).SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a method and an apparatus for producing a thin film, and more particularly to a method and apparatus for producing a thin film by suppressing side reactions. By appropriately reducing the film growth rate and removing process by-products within the thin film, corrosion and degradation can be prevented, and complex Even when forming a thin film on a substrate with a structure, the step coverage and the uniformity of the thin film thickness are greatly improved. The present invention relates to a thin-film manufacturing method and a thin-film manufacturing apparatus that can improve the [Background technology]

[0002] The integration density of memory and non-memory semiconductor devices is increasing day by day, and their structures are becoming more and more complex. As a result, the step coverage is becoming more and more important when depositing various thin films on a substrate. verage) is becoming increasingly important. Semiconductor thin films are made of metal nitrides, metal oxides, metal silicides, etc. Metal nitride thin films include Titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (ZrN), etc. Thin films are commonly used as interconnect materials between doped silicon layers of semiconductors. It is used as a diffusion barrier between aluminum (Al) and copper (Cu) and is also used for titanium. It is used as an adhesion layer when depositing tungsten (W) thin films onto substrates. In order to obtain favorable and uniform physical properties of the thin film deposited on the substrate, it is necessary to form the thin film with a high step height. Coating properties are essential. Therefore, chemical vapor deposition (CVD) is used, which mainly utilizes gas phase reactions. ALD (atomic layer deposition) is a process that utilizes surface reactions rather than vapor deposition. The atomic layer deposition (ALD) process is being used, but Problems remain to be solved in achieving 00% step coverage. It is also used to deposit titanium nitride (TiN), which is a representative of the above metal nitrides. In the case of titanium tetrachloride (TiCl4), process by-products such as chlorides in the thin film produced This residue can cause corrosion of metals such as aluminum, and non-volatile by-products can The resulting problems lead to deterioration of the film quality. Therefore, it is possible to form thin films with complex structures and to manufacture thin films that do not corrode the interlayer wiring material. The reality is that a method needs to be developed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Korean Patent Publication No. 2006-0037241 Summary of the Invention [Problem to be solved by the invention]

[0004] In order to solve the above problems of the conventional technology, the present invention provides a method for growing a thin film by suppressing side reactions. By appropriately lowering the rate and removing process by-products within the thin film, corrosion and deterioration are prevented, and complex structures can be Even when forming a thin film on a substrate having a large thickness, the step coverage and the thickness uniformity of the thin film are greatly improved. The present invention aims to provide a thin-film manufacturing method and a thin-film manufacturing apparatus that can achieve this. The above and other objects of the present invention are all achieved by the present invention described below. It is possible. [Means for solving the problem]

[0005] In order to achieve the above object, the present invention provides a growth compound for forming a thin film represented by the following chemical formula (1): ii) adsorbing the growth inhibitor onto the substrate surface; and The present invention provides a method for producing a thin film, comprising the step of adsorbing a precursor of the thin film based on the metal-based compound. AnBmXo (1) (wherein A is carbon or silicon, and B is hydrogen or alkyl having 1 to 3 carbon atoms.) X is a halogen; n is an integer of 1 to 15; and o is an integer of 1 or more. is a number, m is 0 to 2n+1.) The present invention also relates to an ALD chamber, a first vaporizer for vaporizing a growth inhibitor for forming a thin film, and a vaporizer for vaporizing the growth inhibitor. a first transfer means for transferring the growth inhibitor for thin film formation into the ALD chamber; A second vaporizer for vaporizing the precursor and for transporting the vaporized Ti-based thin film precursor into the ALD chamber. The present invention provides a thin-film manufacturing apparatus including a second transport means. Effect of the Invention

[0006] According to the present invention, the side reaction is suppressed, the deposition rate is reduced, and the thin film growth rate is appropriately reduced. By removing the by-products from the thin-film process, corrosion and deterioration can be prevented, and thin films can be formed on substrates with complex structures. A method for manufacturing a thin film that greatly improves step coverage and thin film thickness uniformity even when forming a film It has the effect of providing. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a process diagram for explaining a conventional ALD process. [Diagram 2] FIG. 1 is a process diagram illustrating an ALD process according to one embodiment of the present invention. [Diagram 3] 1 is a graph showing the change in thin film thickness with increasing ALD cycles for Example 7 (SP-TiCl4) of the present invention and Comparative Example 1 (TiCl4). [Figure 4] 1 is a graph showing the change in deposition rate with the feeding time of a growth inhibitor (SP) for thin film formation per ALD cycle in Examples 7-1 to 7-3 of the present invention and Comparative Example 1. [Diagram 5] 3 is a TEM photograph of the TiN thin films deposited in Example 1 (SP-TiCl4) and Comparative Example 1 (TiCl4). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The inventors applied a Ti-based thin film precursor to the surface of a substrate loaded inside an ALD chamber. Before the adsorption of the compound, a halogen-substituted compound having a specific structure is first adsorbed as a growth inhibitor. In the case of using ethylene oxide, the growth rate of the thin film formed after deposition is low, and the ethylene oxide remains as a process by-product. It was confirmed that the amount of halides was significantly reduced and the step coverage was significantly improved. Through extensive research, the present invention has been completed. The method for producing a thin film of the present invention comprises the steps of: i) forming a thin film by using a growth inhibitor for thin film formation represented by the following chemical formula (1) ii) adsorbing a Ti-based thin film precursor onto the substrate surface on which the growth inhibitor is adsorbed. The process includes a step of adsorbing the body. AnBmXo (1) (wherein A is carbon or silicon, and B is hydrogen or alkyl having 1 to 3 carbon atoms.) X is a halogen; n is an integer of 1 to 15; and o is an integer of 1 or more. is a number, m is 0 to 2n+1.) In such a case, it is necessary to suppress side reactions during thin film formation to reduce the thin film growth rate and to prevent side reactions in the thin film process. By removing the by-products, corrosion and degradation are reduced, and thin films can be formed on substrates with complex structures. Even in such a case, the step coverage and the thickness uniformity of the thin film can be significantly improved.

[0009] The step i) of adsorbing a growth inhibitor for thin film formation on the surface of the substrate is The feeding time of the growth inhibitor is preferably 1 to 10 seconds, more preferably 1 to 10 seconds. Preferably, it is 1 to 5 seconds, more preferably, it is 2 to 5 seconds, and even more preferably, it is 2 to 5 seconds. Within this range, the thin film growth rate is low, and it has the advantages of excellent step coverage and cost-effectiveness. . In this description, the supply time of the growth inhibitor for thin film formation is 15 to 20 times the volume of the chamber. Based on the volume of the chamber of 18 L and the flow rate of 0.5 to 5 mg / s, The standard is a flow rate of 1 to 2 mg / s. The step i) of adsorbing a growth inhibitor for thin film formation onto a substrate surface is preferably carried out by A growth inhibitor for film formation is injected into the ALD chamber and adsorbed onto the loaded substrate surface. In such a case, the deposition rate is slowed down to suppress side reactions and reduce the thin film growth rate. It is also effective in removing process by-products within the thin film. The step i) of adsorbing the growth inhibitor for thin film formation onto the surface of the substrate is preferably carried out by purging the remaining thin film growth inhibitor that is not adsorbed on the substrate with a purge gas. In this case, the side reaction during the thin film formation is suppressed to reduce the thin film growth rate and the by-products in the thin film process. By removing the However, it has the advantage of greatly improving step coverage and the thickness uniformity of the thin film. In addition, the step ii) of adsorbing the Ti-based thin film precursor is preferably carried out by The method includes purging any remaining Ti-based thin film precursor with a purge gas.

[0010] The thin film production method preferably comprises adsorbing a Ti-based thin film precursor onto a substrate surface, and then reacting the Ti-based thin film precursor with a Ti-based thin film precursor. A process of supplying a gas, and a process of purging the reaction by-products of the Ti-based thin film precursor and the reaction gas with a purge gas. The method includes a step of aging. In a preferred embodiment of the thin film manufacturing method, the thin film forming growth inhibitor is vaporized. and adsorbing the ALDP on a surface of a substrate loaded in an ALD chamber; D) a step of purging the inside of the chamber with a purge gas; and c) a step of vaporizing a Ti-based thin film precursor. and adsorbing the ALDP on a surface of the substrate loaded in the ALD chamber; and d) adsorbing the ALDP on a surface of the substrate loaded in the ALD chamber. D) a second purging of the interior of the ALD chamber with a purge gas; and e) a second purging of the interior of the ALD chamber. and f) tertiary purging the interior of the ALD chamber with a purge gas. In such a case, the thin film growth rate is appropriately reduced, and the deposition rate is appropriately reduced during thin film formation. Even at high temperatures, process by-products are effectively removed, reducing the resistivity of the thin film. This has the advantage of greatly improving step coverage.

[0011] The growth inhibitor for thin film formation and the Ti-based thin film precursor are preferably used in a method such as a VFC method or a DLI method. The ALD chamber is preferably transported to the substrate surface by the ALD or LDS method. The sample is transferred into the ALD chamber using the S method. The amount of the growth inhibitor for thin film formation and the precursor compound added to the ALD chamber (mg / cy The ratio of 1:1.5 to 1:20 is preferred, and 1:2 or less is more preferred. Preferably, the ratio is 1:15, more preferably 1:2 to 1:12, and even more preferably 1:2.5 to 1:10, and within this range, the thin film growth rate per cycle (GPC) The reduction rate 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 usually used in ALD. A preferred, but not limiting, example is titanium tetrahalide. The titanium tetrahalides are preferably TiF4, TiCl4, TiBr4 and Ti I4, for example TiCl4. is preferable from the viewpoint of economic efficiency, but the present invention is not limited thereto. However, the titanium tetrahalide has excellent thermal stability and remains in a liquid state without being decomposed at room temperature. Since it exists in a crystalline form, it can be usefully used as a thin film precursor for ALD to deposit thin films. can be done. For example, the Ti-based thin film precursor may be mixed with a non-polar solvent and then 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 non-polar solvent is at least one selected from the group consisting of alkanes and cycloalkanes. In such cases, it is necessary to use an organic solvent that has low reactivity and solubility and is easy to control moisture content. This also has the advantage that step coverage is improved even if the deposition temperature increases during thin film formation. In a more preferred embodiment, the non-polar solvent is a C1 to C10 alkane or a C3 The cycloalkanes include C10 cycloalkanes, and preferably C3 to C10 cycloalkanes. In this case, there are advantages in that the reactivity and solubility are low and the moisture content is easily controlled. In this description, C1, C3 etc. refer to carbon numbers. The cycloalkane is preferably a C3 to C10 monocycloalkane, Among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure. A deposition process is preferred, but is not limited thereto. The non-polar solvent has, for example, a solubility in water (25° C.) of 200 mg / L or less. Preferably, it is 50 to 200 mg / L, more preferably, it is 135 to 175 mg / L. Within this range, the reactivity with Ti-based thin film precursors is low, and moisture control is easy. . In this description, the solubility is measured by the measurement method and standard commonly used in the technical field to which the present invention pertains. As long as the concentration is not particularly limited, a saturated solution can be measured by HPLC, for example. The non-polar solvent is preferably in an amount of 100 to 2000 based on the total weight of the Ti-based thin film precursor and the non-polar solvent. The content is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and even more preferably The content is preferably 40 to 90% by weight, and most preferably 70 to 90% by weight. If the content of the non-polar solvent exceeds the upper limit, it may cause impurities and lead to resistance. When the impurity value in the thin film increases and the organic solvent is added below the lower limit, The effect of adding a solvent on improving step coverage and reducing impurities such as chlorine (Cl) ions There are some disadvantages.

[0013] The thin film manufacturing method may, for example, have a thin film growth rate per cycle calculated by the following Equation 1: The decrease in the rate (angstroms / cycle) is -5% or less, preferably -10% or less, more preferably -20% or less, even more preferably -30% or less, and even more preferably The thickness is preferably -40% or less, and most preferably -45% or less. The coating thickness is excellent and uniform. [Number 1] Decrease rate of thin film growth rate per cycle (%) = [(When using a thin film growth inhibitor Thin film growth rate per cycle - cycles without the use of a thin film growth inhibitor Thin film growth rate per cycle) / Thin film growth rate per cycle when no growth inhibitor for thin film formation was used growth rate]×100 The thin film manufacturing method includes a thin film formed after 200 cycles as measured by SIMS. The strength of residual halogen in the film (c / s) is preferably 10,000 or less, more preferably 8, 000 or less, more preferably 7,000 or less, and even more preferably 6,000 or less. Within this range, the effect of preventing corrosion and deterioration is excellent. In this description, the purging is preferably at 1,000 to 10,000 sccm, more preferably More preferably, it is 2,000 to 7,000 sccm, and even more preferably, it is 2,500 to 6,000sccm, and within this range, the thin film growth rate per cycle is in the preferred range. This has the effect of reducing process by-products.

[0014] The ALD is used for integrated circuits (ICs) that require a high aspect ratio. This is particularly advantageous in the fabrication of semiconductor devices, where the self-limiting thin film growth mechanism The coating method provides excellent conformality and uniform coverage. The advantages of this method include excellent dimensional accuracy and precise thickness control. The thin film manufacturing method is preferably carried out at a deposition temperature in the range of 50 to 900° C., for example. The deposition temperature is preferably in the range of 300 to 700°C, more preferably in the range of 350 to 600°C. The deposition temperature is preferably in the range of 400 to 550° C. More preferably, the deposition temperature is in the range of 400 to 500° C. It is highly effective in growing a thin film with excellent film quality while embodying the characteristics of the ALD process. The thin film manufacturing method is carried out at a deposition pressure ranging from 0.1 to 10 Torr, for example. , preferably at deposition pressures in the range of 0.5 to 5 Torr, most preferably 1 to 3 Torr. The deposition pressure is in the range of rr, and within this range, a thin film of uniform thickness can be obtained. In this description, deposition temperature and deposition pressure refer to the temperature and pressure established in a deposition chamber. This can be measured by the temperature and pressure applied to the substrate in the deposition chamber. This can be done.

[0015] The thin film manufacturing method preferably includes the steps of: and / or a step of increasing the temperature in the chamber to a deposition temperature. and a step of purging the chamber by injecting an inert gas into the chamber before the chamber is loaded. . In addition, the present invention provides a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, which is an ALD method. a chamber, a first vaporizer for vaporizing a growth inhibitor for thin film formation, and a vaporized growth inhibitor for thin film formation. A first transfer means for transferring the agent into the ALD chamber, and a second vaporizer for vaporizing the Ti-based thin film precursor. and a second transport means for transporting the vaporized Ti-based thin film precursor into the ALD chamber. The manufacturing apparatus includes a vaporizer and a transport means that are commonly used in the technical field to which the present invention pertains. There are no particular limitations as long as the vaporizer and transfer means are compatible with the above.

[0016] As a specific example, the thin film manufacturing method will be described below. First, a substrate on which a thin film can be formed is placed in a deposition chamber capable of atomic layer deposition. do. The substrate includes a semiconductor substrate such as a silicon substrate, a silicon oxide substrate, or the like. The substrate may further have a conductive or insulating layer formed thereon. In order to deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned thin film forming device is A growth inhibitor and a Ti-based thin film precursor or a mixture of the Ti-based thin film precursor and a non-polar solvent are each prepared. After that, the prepared thin film formation inhibitor is injected into the vaporizer, and then it is converted into a gas phase and the deposition chamber is formed. The thin film formation inhibitor is transferred to the chamber and adsorbed onto the substrate, and non-adsorbed thin film formation inhibitor is purged. Next, the prepared Ti-based thin film precursor or a mixture of this and a non-polar solvent is injected into the vaporizer. Then, it is converted into a gas phase and transferred to a deposition chamber where it is adsorbed onto a substrate, forming a non-adsorbed thin film. The composition is purged.

[0017] In this description, a thin film formation inhibitor and a Ti-based thin film precursor are delivered to a deposition chamber. One example of the method is a mass flow controller (MFC). A method of transporting volatilized gas using the Vapor Flow Control (FC) method VFC or Liquid Mass Flow Control Liquid Delivery System (Liquid Delivery Facility;LMFC) A Laser Deposition System (LDS) is used, and preferably the LDS method is used. Carrier gas for moving thin film formation inhibitors and Ti-based thin film precursors onto the substrate Alternatively, dilution gas can be selected from argon (Ar), nitrogen (N2), or helium (He). The present invention may use, but is not limited to, one or more of the gases described above. In this description, as an example of a purge gas, an inert gas is used, preferably The above-mentioned carrier gas or diluent gas is used. Next, a reaction gas is supplied. The reaction gas is a gas that is commonly used in the technical field to which the present invention pertains. There is no particular limitation as long as the reaction gas is usable, and preferably contains 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, and the The nitriding agent forms a thin metal nitride film, and the oxidizing agent forms a thin metal oxide film. is formed. Preferably, the reducing agent is ammonia gas (NH3) or hydrogen gas (H2), The nitriding agent is nitrogen gas (N2), and the oxidizing agent is selected from H2O, H2O2, O2, O3, and N2O. The compound is one or more selected from the group consisting of:

[0018] Next, an inert gas is used to purge the remaining unreacted reactant gas. Thus, not only the excess reaction gas but also the by-products that are produced can be removed. In this way, the step of adsorbing the thin film formation inhibitor onto the substrate, a step of purging the substrate, a step of adsorbing a Ti-based thin film precursor onto the substrate, and a step of forming a non-adsorbed thin film. purging the composition for use, supplying a reaction gas, and purging the remaining reaction gas. The process is defined as a unit cycle, and the unit cycle is repeated to form a thin film of a desired thickness. Can be repeated. The unit cycle is, for example, 100 to 1000 times, preferably 100 to 1000 times. The preferred range is 500 times, more preferably 150 to 300 times. This has the effect of allowing the properties to be expressed optimally.

[0019] FIG. 1 is a process diagram for explaining a conventional ALD process, and FIG. 2 is a process diagram for explaining an embodiment of the present invention. FIG. 1 is a process diagram for explaining the ALD process. The growth inhibitor for thin film formation of the present invention is applied to a Ti-based thin film precursor (TiC If the substrate surface is not protected by adsorption before the adsorption of NH3, the reaction gas (NH4) and The thin film (TiN) formed by the reaction contains process by-products such as HCl, causing corrosion and deterioration. However, as shown in FIG. 2, the growth suppressor for thin film formation according to the present invention The inhibitor (TSI) is first adsorbed on the substrate before the Ti-based thin film precursor (TiCl4) is adsorbed. For surface protection (SP), thin film (TiN) During formation, process by-products such as HCl, which reacts with the reaction gas (NH3), form a thin film. This prevents corrosion and deterioration of the substrate by removing the growth inhibitors used, and also improves the durability of the substrate after each cycle. The thin film growth rate can be appropriately reduced to improve step coverage and thin film thickness uniformity. .

[0020] The growth inhibitor for thin film formation of the present invention is preferably a compound represented by chemical formula (1) . AnBmXo (1) (wherein A is carbon or silicon, and B is hydrogen or alkyl having 1 to 3 carbon atoms.) X is a halogen; n is an integer of 1 to 15; and o is an integer of 1 or more. is a number, m is 0 to 2n+1.) In such a case, it is necessary to suppress side reactions during thin film formation to reduce the thin film growth rate and to prevent side reactions in the thin film process. By removing the by-products, corrosion and degradation are reduced, and thin films can be formed on substrates with complex structures. Even in such a case, the step coverage and the thickness uniformity of the thin film can be significantly improved. B is preferably hydrogen or methyl, n is preferably an integer from 2 to 15, more preferably Preferably, an integer between 2 and 10, more preferably an integer between 2 and 6, even more preferably is an integer between 4 and 6. Within this range, the effect of removing process by-products is large, and the step coverage is good. It is excellent. In the chemical formula (1), X is, for example, one selected from the group consisting of F, Cl, Br and I. or more, preferably Cl (chlorine). In this case, side reactions are suppressed to prevent process by-products. It has the effect of effectively removing. In the chemical formula (1), o is preferably an integer of 1 to 5, more preferably It is an integer between 1 and 3, and more preferably 1 or 2. Within this range, The deposition rate is significantly reduced, and the step coverage is more effectively improved. m is preferably 1 to 2n+1, more preferably 3 to 2n+1. Within this range, the effect of removing process by-products is large, and step coverage is excellent.

[0021] The compound of formula (1) is preferably a branched, cyclic or aromatic compound. Specific examples include 1,1-dichloroethane, 1,2-dichloroethane, and dichloromethane. 2-chloropropane, 1-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane Chloropropane, 2,2-dichloropropane, 1-chloropentane, 2-chloropentane , 3-chloropentane, chlorocyclopentane, n-butyl chloride, tert-butyl chloride Chloride, sec-butyl chloride, isobutyl chloride, 1,2-dichlorobenzene, 1 ,4-Dichlorobenzene, Trimethylchlorosilane, Trichloropropane, 2-Chloro- One or more selected from the group consisting of 2-methylbutane, 2-methyl-1-pentane, etc. In this case, there are advantages in that the effect of removing process by-products is large and step coverage is excellent. The compound of formula (1) is preferably used in an ALD process, in which case Ti It effectively protects the substrate surface as a growth inhibitor without inhibiting the adsorption of the precursor of the thin film, and prevents process side effects. This has the advantage of effectively removing the products. The compound represented by the chemical formula (1) is preferably liquid at room temperature (22° C.) and has a density of 0 .8 to 1.5 g / cm 3 and the vapor pressure (20°C) is 1 to 300 mmHg. The solubility in water (25°C) is 200mg / L or less, and within this range, the step coverage and It also has the effect of providing excellent uniformity in the thickness of the thin film. More preferably, the compound represented by Formula 1 has a density of 0.85 to 1.3 g / mol. cm 3 The vapor pressure (20°C) is 1 to 260 mmHg, and the solubility in water ( 25℃) is 160mg / L or less, and within this range, the step coverage and thin film thickness uniformity are ensured. It has excellent effects.

[0022] The semiconductor substrate of the present invention is manufactured by the thin film manufacturing method described herein. By suppressing the reaction and appropriately reducing the thin film growth rate, and removing the process by-products within the thin film, corrosion is reduced. The film has excellent effects in terms of step coverage and uniformity of the thin film thickness. The produced thin film preferably has a thickness of 20 nm or less and a resistivity of 0.1 to 4. 00μΩ·cm, halogen content is 10,000ppm or less, and step coverage is 9 Within this range, the film has excellent performance as a diffusion barrier and reduces corrosion of metal wiring materials. The effects are, but not limited to, The thin film has a thickness of, for example, 5 to 20 nm, preferably 10 to 20 nm, more preferably More preferably, it is 15 to 18.5 nm, and even more preferably, it is 17 to 18.5 nm. Within this range, there is excellent effect on thin film properties. The thin film has a specific resistance of, for example, 0.1 to 400 μΩ·cm, preferably 50 or more. At most 400 μΩ·cm, more preferably 200 to 400 μΩ·cm, and even more preferably is 300 to 400 μΩ cm, more preferably 330 to 380 μΩ cm, The most preferable range is 340 to 370 μΩ·cm. There is fruit. The thin film preferably has a halogen content of 9,000 ppm or less or 1 to 9, 000 ppm, more preferably 8,500 ppm or less or 100 to 8,500 ppm pm, and even more preferably 8,200 ppm or less or 1,000 to 8,200 ppm Within this range, the thin film properties are excellent while reducing corrosion of the metal wiring material. . The thin film has, for example, a step coverage of 80% or more, preferably 90% or more, and more preferably Within this range, even thin films with complex structures can be easily deposited on a substrate. This has the advantage that it can be applied to next-generation semiconductor devices.

[0023] The produced thin film may be, for example, a TiN or TiO2 thin film. In the following, preferred embodiments and drawings are presented to aid in understanding the present invention. The drawings are merely illustrative of the present invention, and various modifications and variations within the scope of the scope and technical concept of the present invention are within the scope of the present invention. It will be apparent to those skilled in the art that variations and modifications may be made. Of course, it also falls 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 used. The prepared growth inhibitor for thin film formation was placed in a canister and placed in LMFC(Li quid Mass Flow Controller) to obtain a flow rate of 0.05g / min. The gas was supplied to a vaporizer heated to 150°C at a flow rate of 1000 g. The growth inhibitor was injected into the deposition chamber with the substrate loaded for 3 seconds, and then argon gas was injected. Argon purging was performed by supplying argon at 3000 sccm for 6 seconds. The pressure in the chamber was controlled at 1.3 Torr. Next, the prepared TiCl4 was placed in a separate canister. It was placed in a furnace and heated to 150℃ at room temperature with a flow rate of 0.05g / min using an LMFC. The TiCl4 vaporized in the vaporizer was then placed in the deposition chamber for 3 seconds. After the mixture was poured into the flask, argon gas was supplied at 3000sccm for 6 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled at 1.3 Torr. Ammonia was injected into the reaction chamber as a gas for 5 seconds, followed by argon perfusion for 10 seconds. In this process, the substrate on which the metal thin film was to be formed was heated to 460°C. The process was repeated 200 times to form a TiN thin film, which is a self-limiting atomic layer. [Table 1]

[0025] Comparative Example 1 In Example 1, no growth inhibitor for thin film formation was used, and as a result, a non-adsorbed thin film was formed. The growth inhibitor was removed from the substrate in the same manner as in Example 1, except that the step of purging the growth inhibitor was omitted. A thin TIN film was formed on the substrate. Comparative Examples 2 and 3 In Example 1, instead of the growth inhibitors for thin film formation listed in Table 1 above, pentane or cyclohexyl A TiN thin film was formed on a substrate in the same manner as in Example 1, except that pentane was used.

[0026] 1) Deposition evaluation Refer to Table 2. Chloro-2-methylbutane is used as a growth inhibitor for thin film formation. The results were compared between Example 1, which used the agent as a coating agent, and Comparative Example 1, which did not contain the agent. The rate was 0.20 angstroms / cycle, which was 55.5% higher than in Comparative Example 1. The remaining Examples 2 to 7 also showed deposition rates similar to those of Example 1. It was confirmed that the growth inhibitor for thin film formation according to the present invention was Comparative Examples 2 and 3, in which pentane or cyclopentane was used, also had the same deposition values ​​as Comparative Example 1. It was confirmed that the decrease in deposition rate was due to the CVD deposition characteristics A This means that the LD deposition characteristics are changed, so it can be used as an indicator of the improvement of step coverage characteristics. It is possible. [Table 2]

[0027] As shown in Table 3, the growth inhibitor for thin film formation, chloro-2-methylb It was confirmed that the deposition rate continuously decreased according to the amount of utane injected. Here, Example 1-1 is the same as Example 1 except for the injection amount of the growth inhibitor for thin film formation per cycle. The same procedure was used for both experiments. [Table 3]

[0028] 2) Impurity reduction properties Impurity reduction characteristics, i.e., process by-products, of TiN thin films deposited in Example 1 and Comparative Example 1 SIMS analysis was performed to compare the reduction characteristics, and the results are shown in Table 4. [Table 4] As shown in Table 4, Example 1, which uses the growth inhibitor for thin film formation according to the present invention, It was confirmed that the level was reduced to 1 / 3 compared to Comparative Example 1, which did not use . FIG. 3 shows the ALD cycles of Example 7 (SP-TiCl4) of the present invention and Comparative Example 1 (TiCl4). 1 is a graph showing the change in the film thickness with increasing the number of droplets. In the case of Example 7, the film thickness is significantly increased. It was confirmed that the thickness of the film had become thinner. FIG. 4 shows the thin films per ALD cycle of Examples 7-1 to 7-3 of the present invention and Comparative Example 1. 1 is a graph showing the change in deposition rate with the feeding time of a growth inhibitor (SP) for formation. In the case of Comparative Example 1 where the thin film formation inhibitor according to the present invention was not used, The deposition rate of the thin film of the present invention was about 0.45 angstroms / cycle. In the case of Examples 7-1, 7-2, and 7-3, the formation inhibitor was added for 0.7 seconds, 1 second, and 2 seconds, respectively. The deposition rates for the two were 0.35 Å / cycle and 0.2 Å / cycle, respectively. It was confirmed that the ion concentration was significantly lowered to 0.1 Å / cycle. Here, Examples 7-1, 7-2, and 7-3 are the same as those of Example 7, except for the growth suppression for thin film formation. The same procedure was followed except for the amount of agent added.

[0029] 3) Step coverage characteristics The TiN thin films deposited in Example 1 and Comparative Example 1 were examined for step coverage using TEM. The results are shown in Table 5 and FIG. [Table 5] As shown in Table 5, Example 1, which uses the growth inhibitor for thin film formation according to the present invention, It was confirmed that the step coverage rate was significantly higher than that of Comparative Example 1, which did not use . In addition, referring to the TEM photograph in FIG. 5, the T deposited in Example 1 (SP-TiCl4) The thickness uniformity of the IN thin film at the top and bottom was compared with that of the IN thin film deposited in Comparative Example 1 (TiCl4). It was confirmed that the step coverage was superior to that of the TIN thin film.

Claims

[Claim 1] i) a step of adsorbing a growth inhibitor for thin film formation represented by the following chemical formula (1) onto a substrate surface; and ii) A method for producing a thin film comprising the step of adsorbing a Ti-based thin film precursor onto the substrate surface to which the growth inhibitor is adsorbed. Membrane manufacturing method. AnBmXo (1) (wherein A is carbon or silicon, and B is hydrogen or alkyl having 1 to 3 carbon atoms.) X is a halogen; n is an integer of 1 to 15; and o is an integer of 1 or more. is a number, m is 0 to 2n+1.

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