Composition for vapor deposition of antimony-containing thin films and method for producing antimony-containing thin films using the same

Abstract

To provide a composition for depositing an antimony-containing thin film including a novel antimony compound which may be useful as a precursor of an antimony-containing thin film and a method for manufacturing an antimony-containing thin film using the same.SOLUTION: There is provided a composition for depositing a thin film that includes an antimony compound represented by the following Chemical Formula 1. In the Chemical Formula 1, R1 to R5 are independently a linear or branched (C1 to C7) alkyl.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to a composition for vapor deposition of an antimony-containing thin film, which contains a novel antimony compound as a precursor of the antimony-containing thin film, and a method for producing an antimony-containing thin film using the composition. [Background technology]

[0002] Antimony (Sb)-containing thin films have excellent thin film properties and are therefore applicable to a wide variety of applications, including insulating films, diffusion barriers, hard masks, etching stop layers, seed layers, spacers, intermetal dielectric materials, protective layers, and anti-reflective layers. In particular, antimony-containing thin films have been attracting attention as next-generation hard mask materials in the EUV photolithography process due to their excellent etching resistance.

[0003] On the other hand, semiconductor circuits have become increasingly miniaturized over the years due to the increasing performance of elements. The miniaturization of semiconductor circuits, the increase in aspect ratio, and the diversification of element materials have created a demand for technology that can form ultra-fine thin films that are uniform and thin even at low temperatures, and that have excellent electrical properties and etching resistance.

[0004] However, conventional antimony-containing thin film precursors are difficult to apply to plastic substrates because they require high-temperature processes, and attempts to lower the process temperature can result in a decrease in the thin film deposition rate and purity of the thin film. They also have limitations such as insufficient step coverage, etching resistance, and physical and electrical properties. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2009-0091107 (2008.05.15.) Summary of the Invention [Problem to be solved by the invention]

[0006] One aspect of the present invention provides a composition for forming an antimony-containing thin film, which can provide a high-quality antimony-containing thin film.

[0007] Another aspect of the present invention provides a method for producing an antimony-containing thin film, which enables deposition of a thin film at a high thin film deposition rate even under mild reaction conditions, and can produce a high-quality antimony-containing thin film with high purity.

[0008] Furthermore, one aspect of the present invention provides an antimony compound with a novel structure that can be usefully used as a precursor for antimony-containing thin films. [Means for solving the problem]

[0009] The present invention provides a composition for forming an antimony-containing thin film, which can produce a high-quality antimony-containing thin film. The composition for vapor deposition of an antimony-containing thin film according to one aspect of the present invention may contain an antimony compound represented by the following Chemical Formula 1:

[0010] [ka] (In the above chemical formula 1, R1 to R5 are each independently a linear or branched (C1-C7) alkyl.

[0011] More preferably, in the above chemical formula 1, R1 to R4 may each independently be a linear (C1-C7) alkyl, and R5 may be a branched (C3-C7) alkyl.

[0012] More preferably, the antimony compound represented by the above chemical formula 1 may be represented by the following chemical formula 2.

[0013] [ka] (In the above chemical formula 2, R 11 and R 12 are, independently of each other, linear or branched (C1-C7) alkyl; R5 is a branched (C3-C7) alkyl.

[0014] More preferably, in the above formula 2, R5 may be a branched (C3-C5) alkyl.

[0015] The antimony compound according to one embodiment may be selected from the following compounds, but is not limited thereto.

[0016] [ka]

[0017] Further, a method for producing an antimony-containing thin film according to one aspect of the present invention includes the steps of: a) maintaining the temperature of the substrate mounted in the chamber at 30 to 500°C; b) contacting a substrate with the antimony-containing thin film deposition composition according to any one of claims 1 to 5 and allowing it to be adsorbed onto the substrate; c) injecting a reaction gas onto the substrate onto which the antimony-containing thin film deposition composition is adsorbed, thereby forming an antimony-containing thin film.

[0018] The reactive gas may include oxygen (O2), ozone (O3), oxygen plasma, hydrogen (H2), hydrogen plasma, water (H2O), hydrogen peroxide (H2O2), nitrogen dioxide (NO2), nitric oxide (NO), nitrous oxide (N2O), ammonia (NH3), carbon dioxide (CO2), formic acid (HCOOH), acetic acid (CH3COOH), acetic anhydride ((CH3CO)2O), or combinations thereof.

[0019] The reactive gas may be supplied after being activated by generating plasma of 50 to 1,000 W.

[0020] Another aspect of the present invention is to provide a novel compound that can be used as a precursor for a high-quality antimony-containing thin film, and the compound may be an antimony compound represented by the following chemical formula 1:

[0021] [ka] (In the above Chemical Formula 1, R1 to R5 are each independently a linear or branched (C1-C7) alkyl.

[0022] More preferably, the antimony compound according to one embodiment may be represented by the following chemical formula 2:

[0023] [ka] (In the above Chemical Formula 2, R 11 and R 12 are, independently of each other, linear or branched (C1-C7) alkyl; R5 is a branched (C3-C7) alkyl. [Effects of the Invention]

[0024] The antimony-containing thin film-forming composition according to one embodiment of the present invention is easy to store and handle, and enables deposition of a thin film at a high thin film deposition rate even at low temperatures, thereby enabling the production of a high-quality antimony-containing thin film with high purity.

[0025] Furthermore, the antimony-containing thin film-forming composition according to one embodiment of the present invention can produce high-quality thin films with high yield, and can be usefully applied to a variety of industrial fields.

[0026] In particular, the antimony compound of the present invention has excellent light absorption rate and light emission effect for EUV, and therefore can be very useful as a hard mask used in the EUV photolithography process. [Brief explanation of the drawings]

[0027] [Figure 1] 1 shows the results of TGA analysis of t-butylbis(dimethylamino)antimony produced in Production Example 1. [Figure 2] 1 shows the results of vapor pressure measurement of t-butylbis(dimethylamino)antimony produced in Production Example 1. [Figure 3] 1 shows the results of TGA analysis of isopropylbis(dimethylamino)antimony produced in Production Example 2. [Figure 4] 1 shows the results of vapor pressure measurement of isopropylbis(dimethylamino)antimony produced in Production Example 2. [Figure 5] 1 is a scanning electron microscope image of a line / space pattern formed on a silicon substrate using the antimony compounds produced in Production Examples 1 and 2. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will now be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein. Furthermore, the scope of protection defined by the claims is not intended to be limited.

[0029] Furthermore, unless otherwise defined, the technical and scientific terms used in the description of the present invention have the meanings that are commonly understood by a person of ordinary skill in the technical field to which this invention belongs, and in the following description, descriptions of well-known functions and configurations that may obscure the gist of the present invention will be omitted.

[0030] Numerical ranges used herein include lower and upper limits, all values ​​within the range, increments logically derived from the form and width of the defined range, all doubly limited values, and all possible combinations of upper and lower limits of numerical ranges limited in different forms. Unless otherwise defined in the specification of the present invention, values ​​outside the numerical range that may occur due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0031] Unless otherwise defined in the present invention, when a part "comprises" a certain element, it means that it may further include other elements, not excluding other elements, unless otherwise specified to the contrary. Furthermore, as used in the specification and the appended claims, the singular form "a," "an," or "an" is intended to include the plural form unless the context dictates otherwise.

[0032] As used herein, the term "alkyl" refers to an organic radical derived from an aliphatic hydrocarbon by removal of one hydrogen and can include both straight-chain and branched alkyls. The alkyl can have 1 to 7, specifically 1 to 5, specifically 1 to 4 carbon atoms. Examples of straight-chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl, while examples of branched alkyls include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, and 2,4-dimethylpentyl.

[0033] The present invention will be specifically described below.

[0034] The composition for depositing an antimony-containing thin film according to one embodiment of the present invention contains a precursor compound having a specific structure, and can provide a high-quality antimony-containing thin film.

[0035] Specifically, the precursor compound according to one embodiment may be an antimony compound represented by the following chemical formula 1:

[0036] [ka] (In the above Chemical Formula 1, R1 to R5 are each independently a linear or branched (C1-C7) alkyl.

[0037] Without being bound by any particular theory, the antimony compound represented by Chemical Formula 1 has the above-described structural characteristics, for example, two amine groups and one alkyl group as substituents, which allows it to exist in a liquid state at room temperature and have excellent reactivity and volatility. As a result, an antimony-containing thin film deposition composition according to one embodiment is easy to store and handle, and is capable of depositing a thin film at a high thin film deposition rate even at low temperatures, thereby providing a high-quality antimony-containing thin film with high purity and excellent durability.

[0038] Furthermore, an antimony-containing thin film produced from an antimony-containing thin film-forming composition according to one embodiment is highly advantageous for forming patterns with smaller feature sizes than currently used chemically amplified resists (CARs). While CARs have high sensitivity, their typical elemental makeup, O, F, S, and C, can make the photoresist excessively transparent at certain wavelengths, thereby reducing sensitivity.

[0039] In addition, chemically amplified resist (CAR) can be difficult to form e-patterns due to roughness issues at small feature sizes, and has the drawback of increasing line edge roughness (LER) as the photospeed decreases, partly due to the nature of the acid catalysis process. In contrast, an antimony compound according to one embodiment of the present invention has excellent light absorption and light emission properties for EUV, making it highly useful as a hard mask for use in EUV photolithography processes.

[0040] Specifically, in Chemical Formula 1 according to one embodiment of the present invention, R1 to R4 may each independently be a linear (C1-C7) alkyl, a linear (C1-C5) alkyl, or a linear (C1-C3) alkyl, for example, methyl, ethyl, or n-propyl. Specifically, R1 and R3 may be the same as each other, and R2 and R4 may be the same as each other, and more specifically, R1 to R4 may be the same as each other.

[0041] In addition, in Chemical Formula 1 according to one embodiment of the present invention, R5 may be a branched (C3-C7) alkyl, for example, R5 may be isopropyl, sec-butyl, isobutyl, tert-butyl, or isopentyl.

[0042] The antimony compound represented by Chemical Formula 1 may be, for example, one represented by Chemical Formula 2 below.

[0043] [ka] (In the above Chemical Formula 2, R 11 and R 12 are, independently of each other, linear or branched (C1-C7) alkyl; R5 is a branched (C3-C7) alkyl.

[0044] Specifically, in the above-mentioned Chemical Formula 2, R 11 and R 12 may each independently be a straight-chain (C1-C7) alkyl, specifically a straight-chain (C1-C5) alkyl, more specifically a straight-chain (C1-C3) alkyl, for example, methyl, ethyl, or n-propyl.

[0045] In addition, in the above Chemical Formula 2, R5 may preferably be a branched (C3-C5) alkyl, such as isopropyl, sec-butyl, isobutyl, tert-butyl, or isopentyl.

[0046] The antimony compound represented by Chemical Formula 1 according to one embodiment has the branched alkyl group R5 introduced as a functional group, and thus has better reactivity and thermal stability as a precursor for antimony-containing thin film deposition, enabling the production of higher quality thin films.

[0047] The antimony compound represented by Chemical Formula 1 may be selected from the following compounds, but is not limited thereto.

[0048] [ka]

[0049] An antimony-containing composition for thin film deposition according to one embodiment necessarily contains the antimony compound represented by Chemical Formula 1 as a precursor for thin film deposition, and the content of the compound represented by Chemical Formula 1 in the composition may be within a range that would be recognizable by a person skilled in the art, taking into consideration the thin film formation conditions, the thickness of the thin film, the properties of the thin film, and the use of the thin film.

[0050] Another aspect of the present invention provides a method for producing an antimony-containing thin film using the antimony-containing thin film deposition composition.

[0051] According to one embodiment, a method for producing an antimony-containing thin film can produce a high-quality antimony-containing thin film at a high deposition rate even at low temperatures and low power by using a composition containing the antimony compound represented by Chemical Formula 1 as a precursor. The antimony-containing thin film can be used in a variety of applications, such as insulating films, diffusion barriers, hard masks, etch stop layers, seed layers, spacers, antireflective layers, intermetal dielectric materials, and passivation layers in the fabrication of electronic devices, and is preferably used as a hard mask in an EUVU photolithography process, but is not limited thereto.

[0052] In the method for producing an antimony-containing thin film according to one embodiment, the thin film deposition method is not particularly limited as long as it is a method commonly used in the art. For example, atomic layer deposition (ALD), chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), or plasma enhanced atomic layer deposition (PEALD) may be used. Specifically, ALD or CVD may be used, but the method is not limited thereto.

[0053] A method for producing an antimony-containing thin film according to one embodiment includes the steps of: a) maintaining the temperature of the substrate mounted in the chamber at 30 to 500°C; b) contacting a substrate with the antimony-containing thin film deposition composition according to one aspect of the present invention and allowing it to be adsorbed onto the substrate; c) injecting a reaction gas onto the substrate onto which the antimony-containing thin film deposition composition is adsorbed, thereby forming an antimony-containing thin film.

[0054] More specifically, the method for producing the antimony-containing thin film includes: a) maintaining the temperature of the substrate mounted in the chamber at 30 to 500°C; b) contacting a substrate with the antimony-containing thin film deposition composition according to one aspect of the present invention and allowing it to be adsorbed onto the substrate; c) purging residual deposition composition and by-products; d) injecting a reaction gas into the substrate onto which the antimony-containing thin film deposition composition is adsorbed to form an antimony-containing thin film; e) purging residual reaction gases and by-products.

[0055] The substrate is not particularly limited as long as it is one commonly used in the field, and may be, for example, a substrate containing one or more semiconductor materials selected from the group consisting of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; an SOI (Silicon On Insulator) substrate; a quartz substrate; or a glass substrate for a display; or a flexible plastic substrate such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), or polyester.

[0056] In addition, the antimony-containing thin film may be formed directly on the substrate, or multiple conductive layers, dielectric layers, or insulating layers may be further formed between the substrate and the antimony-containing thin film.

[0057] For example, the temperature of the substrate may be adjusted to, but is not limited to, 30 to 500°C, 30 to 300°C, or 50 to 200°C.

[0058] For example, the reactive gas may be activated by generating plasma at 50 to 1,000 W, or 100 to 800 W, or 400 to 600 W, before being supplied.

[0059] That is, in the method for producing an antimony-containing thin film according to one embodiment, the compound of Chemical Formula 1 is used as a precursor, so that a thin film can be effectively produced even at a low temperature and with low plasma generation.

[0060] The reaction gas can remove ligands of the antimony compound contained in the antimony-containing thin film deposition composition to form an (Sb—O) atomic layer.

[0061] The type of the reactive gas is not particularly limited as long as it is commonly used in the relevant field, but examples include oxygen (O), ozone (O), oxygen plasma, hydrogen (H), hydrogen plasma, water (H0), hydrogen peroxide (H0), nitrogen dioxide (NO), nitric oxide (NO), nitrous oxide (NO), ammonia (NH), carbon dioxide (CO), formic acid (HCOOH), acetic acid (CHCOOH), acetic anhydride ((CHCO)0), and combinations thereof. The purge gas may be nitrogen (N), argon (Ar), and helium (He), or combinations thereof.

[0062] In one embodiment of the method for producing an antimony-containing thin film, deposition conditions can be adjusted depending on the structure or thermal properties of the target thin film, and deposition conditions according to one embodiment include the supply flow rate of the antimony-containing thin film deposition composition containing the compound of Chemical Formula 1, the supply flow rates of the reactant gas and carrier gas, pressure, RF power, substrate temperature, etc. Non-limiting examples include the supply flow rate of the antimony-containing thin film deposition composition of 10 to 1000 cc / min, the carrier gas of 10 to 1000 cc / min, the reactant gas of 1 to 1500 cc / min, the pressure of 0.5 to 10 torr, and the RF power and substrate temperature as described above.

[0063] In yet another aspect of the present invention, there is provided a novel compound that can be used as a precursor of an antimony-containing thin film. Specifically, the novel compound may be an antimony compound represented by the following Chemical Formula 1:

[0064] [ka] (In the above Chemical Formula 1, R1 to R5 are each independently a linear or branched (C1-C7) alkyl.

[0065] Without being bound by any particular theory, the antimony compound represented by Chemical Formula 1 has the above-described structural characteristics, e.g., two amine groups and one alkyl group as substituents, and thus exists in a liquid state at room temperature and has excellent reactivity, volatility, and thermal stability. As a result, the antimony compound represented by Chemical Formula 1 is easy to store and handle, and when used in an antimony-containing thin film deposition composition, it can produce a high-purity thin film at an excellent thin film deposition rate.

[0066] Specifically, R1 to R4 may each independently be a linear (C1-C7) alkyl, preferably a linear (C1-C5) alkyl, more specifically a linear (C1-C3) alkyl, for example, methyl or ethyl. Specifically, R1 and R3 may be the same as each other, R2 and R4 may be the same as each other, and more specifically, R1 to R4 may be the same as each other.

[0067] In addition, in Chemical Formula 1 according to one embodiment of the present invention, R5 may be a branched (C3-C5) alkyl, for example, R5 may be isopropyl, sec-butyl, isobutyl, tert-butyl, or isopentyl.

[0068] The antimony compound represented by Chemical Formula 1 may be, for example, one represented by Chemical Formula 2 below.

[0069] [ka] (In the above Chemical Formula 2, R 11 and R 12 are, independently of each other, linear or branched (C1-C7) alkyl; R5 is a branched (C3-C7) alkyl.

[0070] Specifically, in the above-mentioned Chemical Formula 2, R 11 and R 12 may be, independently of each other, a linear (C1-C7) alkyl, a linear (C1-C5) alkyl, or a linear (C1-C3) alkyl, such as methyl or ethyl. In addition, in Chemical Formula 2, R5 may be, for example, isopropyl, sec-butyl, isobutyl, tert-butyl, or isopentyl.

[0071] The antimony compound represented by Chemical Formula 1 may be selected from the following compounds, but is not limited thereto.

[0072] [ka]

[0073] Hereinafter, a method for producing the antimony compound represented by Chemical Formula 1 according to one embodiment will be specifically described, but it goes without saying that other methods known to those skilled in the art are also possible. In addition, the organic solvent used here is not limited, and the reaction time and temperature can also be changed within the scope of the invention.

[0074] According to one embodiment, the method for producing the antimony compound may include the steps of: (A) reacting a compound represented by the following chemical formula 11 with compounds represented by the following chemical formulas 12 and 13 to produce a tris(dialkylamino)antimony compound; and (B) reacting the tris(dialkylamino)antimony compound with a compound represented by the following chemical formula 14 or 15 to produce the antimony compound of the chemical formula 1.

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka] (In the above chemical formulas 11 to 15, R1 to R5 are defined as above; X1 and X2 are each independently a halogen; M1 is an alkali metal; M2 is an alkaline earth metal.

[0080] The solvent used in the production method according to one embodiment is a common organic solvent, and may be one or more selected from 1,4-dioxane, dichloromethane (DCM), dichloroethane (DCE), toluene, acetonitrile (MeCN), nitromethane, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), ether, n-hexane, and chlorobenzene (CB), but is not limited to these.

[0081] In one embodiment, step (A) may be carried out at -20 to 0°C for 1 to 10 hours, specifically at -10 to 0°C for 1 to 5 hours, but is not limited thereto and may be varied depending on the type and amount of reactants and solvent. As an example, in Formulas 13 and 14, M1 may be Li.

[0082] In one embodiment, step (B) may be carried out at -30 to 0°C for 1 to 10 hours, specifically at -20 to -10°C for 1 to 5 hours, but is not limited thereto and may be varied depending on the types and amounts of reactants and solvents used. As an example, M2 in Formula 15 may be Mg.

[0083] The above implementation will be described in more detail below with reference to the following examples, which are for illustrative purposes only and are not intended to limit the scope of the invention.

[0084] The physical properties of the following examples were measured as follows.

[0085] 1) Thickness The thickness of the antimony-containing thin film was measured using an ellipsometer (OPTI-PROBE 2600, THERMAL-WAVE).

[0086] 2) Thermal decomposition temperature (T d ) Thermogravimetric analysis (TGA) was used, in which the sample to be analyzed was heated to 500°C at a rate of 10°C / min while nitrogen gas was injected at a pressure of 1.5 bar / min.

[0087] [Production Example 1] Production of t-butylbis(dimethylamino)antimony

[0088] [ka]

[0089] A 500 mL flask was charged with 169 mL (0.41 mol) of n-butyllithium (2.3 M solution in n-hexane), followed by 300 mL of n-hexane and stirring. The internal temperature of the mixture was maintained at -10°C, and 19 g (0.41 mol) of dimethylamine was gradually added. The mixture was then stirred at room temperature (25°C) for 2 hours to synthesize lithium(dimethylamine).

[0090] 30g (0.13mol) of antimony trichloride (SbCl3) was added to a 1L flask, followed by 300ml of ether, and the mixture was stirred while maintaining the internal temperature at -10°C. 21g of prepared lithium (dimethylamine) was gradually added to the flask, and the mixture was stirred at room temperature for 4 hours to synthesize trisdimethylaminoantimony. After synthesis, lithium chloride (LiCl) was removed using a filter, and the solvent was removed under vacuum. 300mL of hexane was added, and the mixture was stirred while maintaining the internal temperature at -20°C.

[0091] 65 ml (0.13 mol) of t-butylmagnesium chloride (2.0 M solution in ether) was gradually added to the flask while maintaining the internal temperature at -20°C, and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the solvent and by-products were removed under reduced pressure. Then, the mixture was purified at 30°C and 0.4 Torr pressure to synthesize 15 g of t-butylbis(dimethylamino)antimony. 1 H-NMR(C6D6): δ 2.78(s, 12H), δ 1.19(s, 9H)

[0092] [Production Example 2] Production of isopropylbis(dimethylamino)antimony

[0093] [ka]

[0094] The same procedure as in Preparation Example 1 was carried out, except that 186 ml (0.13 mol) of isopropyllithium (0.7 M solution in pentane) was used instead of t-butylmagnesium chloride, to obtain 14 g of isopropylbis(dimethylamino)antimony. 1 H NMR (C6D6): δ 2.85(s, 12H), δ 1.80(st, 1H)δ 1.18(d,6H)

[0095] Figure 1 shows the TGA analysis results for t-butylbis(dimethylamino)antimony prepared in Preparation Example 1. Referring to Figure 1, it can be seen that the antimony compound of Preparation Example 1 has a single evaporation step at about 120°C, and the residue mass at 500°C was confirmed to be 0.9%, indicating that it exhibits fast evaporation characteristics and is evaporated at over 99% without thermal decomposition. These results demonstrate that the antimony compound of Preparation Example 1 has excellent thermal stability.

[0096] FIG. 2 shows the results of measuring the vapor pressure of t-butylbis(dimethylamino)antimony produced in Production Example 1 to confirm its vapor pressure characteristics.

[0097] Figure 3 shows the TGA analysis results for isopropylbis(dimethylamino)antimony prepared in Preparation Example 2. Referring to Figure 3, it can be seen that the antimony compound of Preparation Example 2 has a single evaporation step at about 95°C, and the residue mass at 500°C was confirmed to be 0.2%, indicating that it exhibits fast evaporation characteristics and is evaporated at over 99% without thermal decomposition. These results demonstrate that the antimony compound of Preparation Example 2 has excellent thermal stability.

[0098] FIG. 4 shows the results of measuring the vapor pressure of isopropylbis(dimethylamino)antimony produced in Production Example 2 to confirm its vapor pressure characteristics.

[0099] [Example 1] Antimony oxide thin films were fabricated by plasma enhanced atomic layer deposition (PEA). The precursors used were t-butylbis(dimethylamino)antimony (prepared in Preparation Example 1) and isopropylbis(dimethylamino)antimony (prepared in Preparation Example 2), and oxygen gas was used as the reactant gas.

[0100] A silicon substrate was used as the substrate on which the antimony oxide thin film was to be formed. The silicon substrate was transferred into a deposition chamber and maintained at a constant temperature as shown in Table 1 below.

[0101] The temperature of the stainless steel bubbler-type canister filled with the precursor was maintained to achieve a constant precursor vapor pressure as shown in Table 1. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. A purging process was then performed using argon gas. A reaction process was performed using oxygen gas as the reactive gas at a constant plasma power as shown in Table 1 below. In addition, a purging process was performed using argon gas to remove reaction by-products. The above atomic layer deposition process constituted one cycle, and a certain cycle was repeated to form an antimony oxide thin film. Detailed evaluation conditions and results are shown in Table 1.

[0102] The composition of the antimony oxide thin film was analyzed by X-ray photoelectron spectroscopy, and no carbon or nitrogen was detected, confirming that a pure antimony oxide thin film was obtained.

[0103] [Table 1] JPEG0007738107000020.jpg148170

[0104] [Example 2] Antimony oxide thin films were fabricated by atomic layer deposition using t-butylbis(dimethylamino)antimony prepared in Preparation Example 1 and isopropylbis(dimethylamino)antimony prepared in Preparation Example 2 as precursors, and ozone gas as a reactive gas.

[0105] A silicon substrate was used as the substrate on which the antimony oxide thin film was to be formed, and the silicon substrate was transferred into a deposition chamber and maintained at a constant temperature as shown in Table 2 below.

[0106] The stainless steel bubbler-type canister filled with the precursor was maintained at a temperature to achieve a constant precursor vapor pressure as shown in Table 2 below. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. A purge process was then performed using argon gas, followed by a reaction process using ozone gas as a reactive gas. A purge process was also performed using argon gas to remove reaction by-products. The above atomic layer deposition process constituted one cycle, and a certain number of cycles were repeated to form an antimony oxide thin film. Detailed evaluation conditions and results are shown in Table 2.

[0107] The composition of the antimony oxide thin film was analyzed by X-ray photoelectron spectroscopy, and no carbon or nitrogen was detected, confirming that a pure antimony oxide thin film was obtained.

[0108] [Table 2]

[0109] [Example 3] Antimony-containing thin films were prepared by plasma enhanced atomic layer deposition (PEA) using t-butylbis(dimethylamino)antimony prepared in Preparation Example 1 and isopropylbis(dimethylamino)antimony prepared in Preparation Example 2 as precursors, and carbon dioxide gas as reactant gas.

[0110] A silicon substrate was used as the substrate on which the antimony-containing thin film was to be formed, and the silicon substrate was transferred into a deposition chamber and maintained at a constant temperature as shown in Table 3 below.

[0111] The temperature of the stainless steel bubbler-type canister filled with the precursor was maintained to achieve a constant precursor vapor pressure as shown in Table 3 below. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. A purging process was then performed using argon gas. A reaction process was performed using carbon dioxide gas as the reactive gas at a constant plasma power as shown in Table 3 below. A purging process was also performed using argon gas to remove reaction by-products. The atomic layer deposition process described above constituted one cycle, and a certain cycle was repeated to form an antimony-containing thin film. Detailed evaluation conditions and results are shown in Table 3.

[0112] The composition of the antimony-containing thin film was analyzed by X-ray photoelectron spectroscopy, and it was confirmed that the thin film contained 10% or more of carbon.

[0113] [Table 3] JPEG0007738107000023.jpg149170 [Example 4] Antimony-containing thin films were prepared by chemical vapor deposition using t-butylbis(dimethylamino)antimony prepared in Preparation Example 1 and isopropylbis(dimethylamino)antimony prepared in Preparation Example 2 as precursors, and water vapor as a reactant gas.

[0114] A silicon substrate was used as the substrate on which the antimony-containing thin film was to be formed, and the silicon substrate was transferred into a deposition chamber and maintained at a constant temperature as shown in Table 4 below.

[0115] The temperature of a stainless steel bubbler-type canister filled with the precursor was maintained to a constant precursor vapor pressure as shown in Table 4 below. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas. The reaction gas, water vapor, was transferred into the chamber using argon gas as a carrier gas while the temperature of a stainless steel bubbler-type canister filled with water was maintained to a constant vapor pressure as shown in Table 4 below. The process pressure was adjusted using a throttle valve to maintain a constant chamber pressure. A chemical vapor deposition method was performed using the precursor and water vapor to form an antimony-containing thin film. Detailed evaluation conditions and results are shown in Table 4.

[0116] The composition of the antimony-containing thin film was analyzed by X-ray photoelectron spectroscopy, and it was confirmed that the thin film contained 10% or more of carbon.

[0117] [Table 4]

[0118] <Patterning of antimony-containing thin films> [Example 5] The antimony-containing thin film prepared in Example 3 was used to pattern the antimony-containing thin film.

[0119] Approximately 76 mJ / cm2 in an extreme ultraviolet (EUV) lithography tool to form 1:1 line-space features at a 24 nm pitch 2 The film was patterned using EUV with an exposure of 1000 Hz. It was then baked at 150°C for 3 minutes, developed with 2-heptanone for 15 seconds, and washed with the same solvent.

[0120] Figure 5 shows scanning electron microscope images of line / space patterns formed on a silicon substrate with a pitch of 24 nm. Figure 5(a) shows an image of the pattern using t-butylbis(dimethylamino)antimony from Production Example 1, and Figure 5(b) shows an image of the pattern using isopropylbis(dimethylamino)antimony from Production Example 2.

[0121] As can be seen from the pattern image, a 1:1 line / space pattern is formed uniformly even at a narrow pitch of 24 nm.

Claims

1. An antimony-containing thin film deposition composition comprising an antimony compound represented by the following chemical formula 1: 【Chemical Formula 1】 (In the above Chemical Formula 1, R １ R to R4 are each independently a linear or branched (C1-C7) alkyl, and R is a branched (C3-C7) alkyl.

2. In the above formula 1, R １ ~R ４ and each independently represent a linear (C1-C7) alkyl.

3. The antimony-containing thin film deposition composition according to claim 1 , which is represented by the following chemical formula 2: 【Chemistry 2】 (In the above chemical formula 2, R １１ and R １２ are each independently a linear or branched (C1-C7) alkyl; R ５ is a branched (C3-C7) alkyl.

4. R ５ 4. The antimony-containing thin film deposition composition according to claim 3, wherein is a branched (C3-C5) alkyl.

5. 2. The antimony-containing thin film deposition composition according to claim 1, wherein the antimony-containing thin film deposition composition is selected from the following compounds: 【Chemistry 3】

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