Composition for vapor deposition of antimony-containing thin film, method for manufacturing antimony-containing thin film, and antimony compound

Abstract

The present invention relates to an antimony-containing thin film evaporation composition containing a novel antimony compound that can be effectively used as a precursor for an antimony-containing thin film, and a method for producing an antimony-containing thin film using the same.

Description

Technical Field

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

[0002] Antimony (Sb)-containing thin films can be used as insulating films, anti-diffusion films, hard masks, etch stop layers, seed layers, spacers, intermetal dielectrics, and protective film layers, anti-reflection layers, etc. due to their excellent thin film properties, and their application fields are becoming more diverse. In particular, the antimony-containing thin film has excellent etch resistance, and thus has attracted much attention as a new generation material for a hard mask in an EUV lithography process.

[0003] On the other hand, due to the high performance of components, semiconductor circuits are being miniaturized year by year. Due to the miniaturization of semiconductor circuits, an increase in the aspect ratio, and the diversification of component materials, a technology capable of forming an ultra-fine thin film that is uniform and thin even at low temperatures, and has excellent electrical properties and etch resistance is required.

[0004] However, the precursors of existing antimony-containing thin films are difficult to be applied to plastic substrates along with high-temperature processes. If the process temperature is to be lowered, the thin film vapor deposition rate and the purity of the thin film may be reduced, and there are limitations in step coverage, etch resistance, physical and electrical properties being insufficient.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Korean Patent Publication No. 10-2009-0091107 (May 15, 2008) Summary of the Invention

[0008] Problems to be Solved

[0009] One aspect of the present invention provides a composition for forming an antimony-containing thin film that can provide a high-quality antimony-containing thin film.

[0010] In addition, one aspect of the present invention provides a method for manufacturing an antimony-containing thin film that can vapor-deposit a thin film at a high thin film vapor deposition rate even under mild reaction conditions and can manufacture a high-quality antimony-containing thin film with high purity.

[0011] In addition, one aspect of the present invention provides an antimony compound having a new structure that can be effectively used as a precursor of an antimony-containing thin film.

[0012] Means for Solving the Problems

[0013] The present invention provides a composition for forming an antimony-containing thin film capable of manufacturing a high-quality antimony-containing thin film. The composition for vapor deposition of an antimony-containing thin film according to one embodiment of the present invention may contain an antimony compound represented by the following Chemical Formula 1.

[0014] [Chemical Formula 1]

[0015]

[0016] (In the above Chemical Formula 1,

[0017] R1 to R5 are each independently a linear or branched (C1-C7) alkyl group.)

[0018] More preferably, in the above Chemical Formula 1, R1 to R4 may each independently be a linear (C1-C7) alkyl group, and R5 may be a branched (C3-C7) alkyl group.

[0019] More preferably, the antimony compound represented by the above Chemical Formula 1 may be represented by the following Chemical Formula 2.

[0020] [Chemical Formula 2]

[0021]

[0022] (In the above Chemical Formula 2,

[0023] R 11 and R 12 are each independently a linear or branched (C1-C7) alkyl group;

[0024] R5 is a branched (C3-C7) alkyl group.)

[0025] More preferably, in the above Chemical Formula 2, R5 may be a branched (C3-C5) alkyl group.

[0026] The antimony compound according to one embodiment may be selected from the following compounds, but is not limited thereto.

[0027]

[0028] In addition, a method for manufacturing an antimony-containing thin film according to one embodiment of the present invention may include:

[0029] a) a step of maintaining the temperature of a substrate installed in a chamber at 30 to 500 °C;

[0030] b) a step of bringing the composition for vapor deposition of an antimony-containing thin film into contact with the substrate to adsorb it to the substrate; and

[0031] c) a step of injecting a reaction gas into the substrate adsorbed with the composition for vapor deposition of an antimony-containing thin film to form an antimony-containing thin film.

[0032] The above reaction 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 a combination thereof.

[0033] The above reaction gas may be supplied after generating and activating a plasma of 50 to 1,000 W.

[0034] In addition, one aspect of the present invention provides a novel compound that can be used as a precursor for a high-quality antimony-containing film, and the above compound may be an antimony compound represented by the following Chemical Formula 1.

[0035] [Chemical Formula 1]

[0036]

[0037] (In the above Chemical Formula 1,

[0038] R1 to R5 are each independently a linear or branched (C1-C7) alkyl group.)

[0039] More preferably, the above antimony compound of one aspect may be represented by the following Chemical Formula 2.

[0040] [Chemical Formula 2]

[0041]

[0042] (In the above Chemical Formula 2,

[0043] R 11 and R 12 are each independently a linear or branched (C1-C7) alkyl group;

[0044] R5 is a branched (C3-C7) alkyl group.)

[0045] Advantages of the Invention

[0046] The composition for forming an antimony-containing film according to one aspect of the present invention can be easily stored and processed, can deposit a film at a high film deposition rate even under low-temperature conditions, and can manufacture a high-quality antimony-containing film with high purity.

[0047] In addition, the composition for forming an antimony-containing film according to one aspect of the present invention can manufacture a high-quality film with a high yield and can be effectively applied to various industrial fields.

[0048] In particular, the antimony compound of the present invention has excellent light absorption rate and luminescence effect for EUV, and can be very effectively used as a hard mask used in the EUV lithography process. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 It is the TGA analysis result of tert-butylbis(dimethylamino)antimony manufactured in Production Example 1.

[0050] Figure 2 It is the vapor pressure measurement result of tert-butylbis(dimethylamino)antimony manufactured in Production Example 1.

[0051] Figure 3 It is the TGA analysis result of isopropylbis(dimethylamino)antimony manufactured in Production Example 2.

[0052] Figure 4 It is the vapor pressure measurement result of isopropylbis(dimethylamino)antimony manufactured in Production Example 2.

[0053] Figure 5 It is the SEM image photograph of the line / space pattern formed on a silicon substrate using the antimony compounds manufactured in Production Examples 1 and 2. DETAILED DESCRIPTION

[0054] Hereinafter, the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily implement it. However, the present invention can be implemented in various different ways and is not limited to the embodiments described herein. In addition, it is not intended to limit the scope of protection defined by the claims.

[0055] In addition, technical terms and scientific terms used in the description of the present invention have the meanings generally understood by those skilled in the art to which the present invention pertains unless otherwise defined, and well-known functions and configurations that may unnecessarily confuse the gist of the present invention will be omitted in the following description.

[0056] The numerical ranges used in this specification include upper and lower limits and all values within their ranges, increments logically derived from the form and width of the defined range, all values with double limits, and all possible combinations of the upper and lower limits of numerical ranges defined in different ways. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range.

[0057] Unless otherwise defined in the present invention, the meaning of a part "comprising" a certain component is that, in the absence of a particularly contrary record, other components can be further included, rather than excluding other components. In addition, the singular forms used in the description and the appended claims also mean the plural forms in the context where there is no special indication.

[0058] The term "alkyl" in this specification is an organic radical derived from an aliphatic hydrocarbon by removing one hydrogen, and can include all linear and branched alkyls. The above alkyl can have 1 to 7, specifically 1 to 5, specifically 1 to 4 carbon atoms. The above linear alkyls include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and the above branched alkyls include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, etc., but are not limited thereto.

[0059] Hereinafter, the present invention will be specifically described.

[0060] The composition for vapor deposition of an antimony-containing film according to one embodiment of the present invention contains a precursor compound having a specific structure, and thus can provide a high-quality antimony-containing film.

[0061] Specifically, the above precursor compound in one embodiment can be an antimony compound represented by the following Chemical Formula 1.

[0062] [Chemical Formula 1]

[0063]

[0064] (In the above Chemical Formula 1,

[0065] R1 to R5 are each independently a linear or branched (C1-C7) alkyl.)

[0066] Without being limited to a specific theory, the antimony compound represented by the above Chemical Formula 1 has the above-described structural characteristics, for example, having two amino groups and one alkyl group as substituents, and thus can exist in a liquid state at room temperature, having excellent reactivity and volatility. Accordingly, the composition for vapor deposition of an antimony-containing film in one embodiment can be easily stored and processed, and can vapor-deposit a film at a high film vapor deposition rate even under low-temperature conditions, and can provide a high-quality antimony-containing film having high purity and excellent durability.

[0067] In addition, an antimony-containing film produced from a composition for forming an antimony-containing film of one type is very advantageous for forming a pattern with a smaller feature size compared to currently used chemically amplified resists (CARs). Although CARs (chemically amplified resists) have high sensitivity, their typical elemental makeup of O, F, S, and C makes the resists overly transparent at specific wavelengths, resulting in the drawback of reduced sensitivity.

[0068] In addition, CARs (chemically amplified resists) have the following drawbacks: it may be difficult to form a pattern in small feature sizes due to roughness problems, and partly due to the nature of the acid catalysis process, line edge roughness (LER) increases as photospeed decreases. On the other hand, the antimony compound of an embodiment of the present invention has excellent light absorption rate and luminescence effect for EUV, and thus can be very effectively used as a hard mask used in EUV lithography processes.

[0069] Specifically, in Formula 1 of an embodiment of the present invention, each of R1 to R4 may independently be a linear (C1-C7) alkyl group, or may be a linear (C1-C5) alkyl group, or may be a linear (C1-C3) alkyl group. For example, it may be a methyl group, an ethyl group, or a n-propyl group. Specifically, R1 and R3 may be the same as each other, and R2 and R4 may be the same as each other. More specifically, R1 to R4 may be the same as each other.

[0070] In addition, in Formula 1 of an embodiment of the present invention, R5 may be a branched (C3-C7) alkyl group. For example, R5 may be an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, or an isopentyl group.

[0071] The antimony compound represented by Formula 1 above may be represented, for example, by the following Formula 2.

[0072] [Formula 2]

[0073]

[0074] (In the above Formula 2,

[0075] R 11 and R 12 are each independently a linear or branched (C1-C7) alkyl group;

[0076] R5 is a branched (C3-C7) alkyl group.)

[0077] Specifically, in the above chemical formula 2, R 11 and R 12 each independently may be a linear (C1-C7) alkyl group, specifically may be a linear (C1-C5) alkyl group, more specifically may be a linear (C1-C3) alkyl group. For example, it may be a methyl group, an ethyl group, or a n-propyl group.

[0078] In addition, in the above chemical formula 2, R5 preferably may be a branched (C3-C5) alkyl group. For example, it may be an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, or an isopentyl group.

[0079] Since the antimony compound represented by the above chemical formula 1 of one embodiment introduces the above-mentioned R5 branched alkyl group as a functional group, as a precursor for vapor deposition of an antimony-containing thin film, it can have more excellent reactivity and thermal stability to manufacture a higher-quality thin film.

[0080] The antimony compound represented by the above chemical formula 1 may be selected from the following compounds, for example, but is not limited thereto.

[0081]

[0082] The composition for vapor deposition of an antimony-containing thin film of one embodiment must contain the antimony compound represented by the above chemical formula 1 as a precursor for vapor deposition of the thin film. Considering the film formation conditions of the thin film, the thickness of the thin film, the characteristics of the thin film, the use of the thin film, etc., the content of the compound represented by the above chemical formula 1 in the composition may be within the range recognized by those skilled in the art.

[0083] In addition, another embodiment of the present invention provides a method for manufacturing an antimony-containing thin film using the above composition for vapor deposition of an antimony-containing thin film.

[0084] The method for manufacturing an antimony-containing thin film of one embodiment uses a composition containing the antimony compound represented by the above chemical formula 1 as a precursor, so that a high-quality antimony-containing thin film can be manufactured at a high vapor deposition rate even at low temperature and low power. The above antimony-containing thin film can be used as an insulating film, an anti-diffusion film, a hard mask, an etch stop layer, a seed layer, a spacer, an anti-reflection layer, an intermetal dielectric, and a protective film layer, etc. in various applications, for example, in the production of electronic components, and preferably can be used as a hard mask used in the EUV lithography process, but is not limited thereto.

[0085] In a method for manufacturing an antimony-containing thin film according to one embodiment, the method for depositing the thin film 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), metalorganic chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), or plasma enhanced atomic layer deposition (PEALD) can be used. Specifically, ALD or CVD can be used, but it is not limited thereto.

[0086] A method for manufacturing an antimony-containing thin film according to one embodiment may include:

[0087] a) A step of maintaining the temperature of a substrate installed in a chamber at 30 to 500 °C;

[0088] b) A step of bringing the composition for depositing an antimony-containing thin film according to one embodiment of the present invention into contact with the substrate so that it adsorbs onto the substrate; and

[0089] c) A step of injecting a reaction gas into the substrate adsorbed with the composition for depositing an antimony-containing thin film to form an antimony-containing thin film.

[0090] More specifically, the method for manufacturing the antimony-containing thin film may include:

[0091] a) A step of maintaining the temperature of a substrate installed in a chamber at 30 to 500 °C;

[0092] b) A step of bringing the composition for depositing an antimony-containing thin film according to one embodiment of the present invention into contact with the substrate so that it adsorbs onto the substrate;

[0093] c) A step of purifying the remaining composition for deposition and by-products;

[0094] d) A step of injecting a reaction gas into the substrate adsorbed with the composition for depositing an antimony-containing thin film to form an antimony-containing thin film; and

[0095] e) A step of purifying the remaining reaction gas and by-products.

[0096] The above-mentioned substrate is not particularly limited as long as it is a substrate commonly used in the art. For example, it can be: a substrate containing one or more semiconductor materials such as 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; a flexible plastic substrate such as polyimide (PI, polyimide), polyethylene terephthalate (PET, PolyEthylene Terephthalate), polyethylene naphthalate (PEN, PolyEthylene Naphthalate), polymethyl methacrylate (PMMA, Poly MethylMethAcrylate), polycarbonate (PC, PolyCarbonate), polyethersulfone (PES), polyester (Polyester).

[0097] In addition, regarding the above-mentioned antimony-containing film, in addition to directly forming the film on the above-mentioned substrate, a plurality of conductive layers, dielectric layers, or insulating layers can be further formed between the above-mentioned substrate and the above-mentioned antimony-containing film.

[0098] As an example, the temperature of the above-mentioned substrate can be adjusted to 30 to 500 °C, or 30 to 300 °C, or 50 to 200 °C, but is not limited thereto.

[0099] As an example, the above-mentioned reaction gas can be supplied after generating and activating a plasma of 50 to 1,000 W, or 100 to 800 W, or 400 to 600 W.

[0100] That is, a method for manufacturing an antimony-containing film according to one embodiment can effectively manufacture a film even at low temperature and low plasma generation by using the compound of the above chemical formula 1 as a precursor.

[0101] The above-mentioned reaction gas can remove the ligand of the antimony compound contained in the composition for vapor deposition of the above-mentioned antimony-containing film to form an (Sb-O) atomic layer.

[0102] The type of the above-mentioned reaction gas is not particularly limited as long as it is a gas commonly used in the art. As an example, it can be 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 a combination thereof. The gas for purification can be nitrogen (N2), argon (Ar), helium (He), or a combination thereof.

[0103] The manufacturing method of the antimony-containing thin film of one mode can adjust the evaporation conditions according to the target thin film structure or thermal characteristics. As the evaporation conditions of one mode, the input flow rate of the antimony-containing thin film evaporation composition containing the compound represented by the above Chemical Formula 1, the reaction gas, the input flow rate of the carrier gas, the pressure, the RF power, the substrate temperature, etc. can be exemplified. As a non-limiting example, the input flow rate of the antimony-containing thin film evaporation composition is 10 to 1000 cc / min, the flow rate of the carrier gas is 10 to 1000 cc / min, the flow rate of the reaction gas is 1 to 1500 cc / min, the pressure is 0.5 to 10 torr, and the RF power and the substrate temperature are as described above.

[0104] In addition, another mode of the present invention provides a novel compound that can be used as a precursor of the antimony-containing thin film. Specifically, the above novel compound can be an antimony compound represented by the following Chemical Formula 1.

[0105] [Chemical Formula 1]

[0106]

[0107] (In the above Chemical Formula 1,

[0108] R1 to R5 are each independently a linear or branched (C1-C7) alkyl group.)

[0109] Without being limited to a specific theory, the antimony compound represented by the above Chemical Formula 1 has the structural characteristics as described above. For example, it has two amino groups and one alkyl group as substituents, so it can exist in a liquid state at room temperature, has excellent reactivity, volatility and excellent thermal stability. Thus, the antimony-containing thin film evaporation composition of one mode can be easily stored and processed, and can evaporate the thin film at a high thin film evaporation rate even under low temperature conditions, and can improve the high-quality antimony-containing thin film with high purity and excellent durability. Thus, the antimony compound represented by the above Chemical Formula 1 is easy to store and process, and when applied as an antimony-containing thin film evaporation composition, it can manufacture a high-purity thin film at an excellent thin film evaporation speed.

[0110] Specifically, each of the above R1 to R4 can independently be a linear (C1-C7) alkyl group, preferably a linear (C1-C5) alkyl group, and more specifically a linear (C1-C3) alkyl group. For example, it can be a methyl group or an ethyl group. Specifically, the above R1 and R3 can be the same as each other, R2 and R4 can be the same as each other, and more specifically, the above R1 to R4 can be the same as each other.

[0111] In addition, in Chemical Formula 1 of an embodiment of the present invention, the above R5 can be a branched (C3-C5) alkyl group. For example, the above R5 can be an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group or an isopentyl group.

[0112] The antimony compound represented by the above Chemical Formula 1 can be represented by the following Chemical Formula 2, for example.

[0113] [Chemical Formula 2]

[0114]

[0115] (In the above Chemical Formula 2,

[0116] R 11 and R12 are each independently a linear or branched (C1-C7) alkyl group;

[0117] R5 is a branched (C3-C7) alkyl group.)

[0118] Specifically, in the above Chemical Formula 2, R 11 and R 12 can each independently be a linear (C1-C7) alkyl group, or can be a linear (C1-C5) alkyl group, or can be a linear (C1-C3) alkyl group. For example, it can be a methyl group or an ethyl group. In addition, in the above Chemical Formula 2, R5 can be an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, or an isopentyl group, for example.

[0119] The antimony compound represented by the above Chemical Formula 1 can be selected from the following compounds, for example, but is not limited thereto.

[0120]

[0121] Hereinafter, a method for manufacturing the antimony compound represented by the above Chemical Formula 1 in one embodiment will be specifically described. Of course, it can also be synthesized by methods other than those recognized by those of ordinary skill in the art. The organic solvent used herein is not limited, and of course, the reaction time and temperature can also be changed within the scope not departing from the core of the invention.

[0122] A method for manufacturing the antimony compound in one embodiment may include: (A) a step of reacting a compound represented by the following Chemical Formula 11 with compounds represented by the following Chemical Formula 12 and Chemical Formula 13 to produce a trisdialkylaminoantimony compound; and (B) a step of reacting the above trisdialkylaminoantimony compound with a compound represented by the following Chemical Formula 14 or Chemical Formula 15 to produce the antimony compound represented by the above Chemical Formula 1.

[0123] [Chemical Formula 11]

[0124]

[0125] [Chemical Formula 12]

[0126] M1(NR1R2)

[0127] [Chemical formula 13]

[0128] M1(NR3R4)

[0129] [Chemical formula 14]

[0130] M1R5

[0131] [Chemical formula 15]

[0132] R5M2X2

[0133] (In the above Chemical formulas 11 to 15,

[0134] R1 to R5 are defined as described above;

[0135] X1 and X2 are each independently a halogen;

[0136] M1 is an alkali metal;

[0137] M2 is an alkaline earth metal.)

[0138] The solvent used in one method of manufacturing is a common organic solvent, and can 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, but is not limited thereto.

[0139] One method of the above step (A) can be carried out at - 20 to 0 °C for 1 hour to 10 hours. Specifically, it can be carried out at - 10 to 0 °C for 1 to 5 hours, but is not limited thereto, and can be changed according to the types and amounts of reactants and solvents used. Additionally, as an example, in the above Chemical formulas 13 and 14, M1 can be Li.

[0140] One method of the above step (B) can be carried out at - 30 to 0 °C for 1 hour to 10 hours. Specifically, it can be carried out at - 20 to - 10 °C for 1 to 5 hours, but is not limited thereto, and can be changed according to the types and amounts of reactants and solvents used. Additionally, as an example, in the above Chemical formula 15, M2 can be Mg.

[0141] Hereinafter, the above embodiments will be described in more detail by way of examples. However, the following examples are for illustrative purposes only and do not limit the scope of the claims.

[0142] The physical properties of the following examples were measured as follows.

[0143] 1) Thickness

[0144] The thickness of the antimony-containing film was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE).

[0145] 2) Thermal decomposition temperature (T d )

[0146] The thermogravimetric analysis (TGA) method was used. The above TGA method was measured while heating the sample to be analyzed at a rate of 10 °C / min to 500 °C and injecting nitrogen at a pressure of 1.5 bar / min.

[0147] [Production Example 1] Production of tert-butylbis(dimethylamino)antimony

[0148]

[0149] 169 ml (0.41 mol) of n-butyllithium (2.3 M n-hexane solution) was placed in a 500 mL flask, and then 300 ml of n-hexane was added and stirred. The internal temperature of the above mixture was maintained at -10 °C, and 19 g (0.41 mol) of dimethylamine was slowly added. After that, it was stirred at room temperature (25 °C) for 2 hours to synthesize lithium (dimethylamine) (Li(Dimethylamine)).

[0150] 30 g (0.13 mol) of antimony trichloride (SbCl3) was placed in a 1 L flask, and then 300 ml of ether was added. The internal temperature was maintained at -10 °C and stirred. 21 g of the prepared lithium (dimethylamine) was slowly added to the above flask, and it was stirred at room temperature for 4 hours to synthesize tris(dimethylamino)antimony. After synthesis, lithium chloride (LiCl) was removed by filtration, and the solvent was removed under vacuum. Then, 300 mL of hexane was added, and the internal temperature was maintained at -20 °C and stirred.

[0151] 65 ml (0.13 mol) of t-butylmagnesium chloride (2.0 M ether solution) was slowly added to the above flask while maintaining the internal temperature at -20 °C, and it was stirred at room temperature for 4 hours. After the reaction was completed, the solvent and by-products were removed under reduced pressure. Then, it was refined at a temperature of 30 °C and a pressure of 0.4 Torr to synthesize 15 g of tert-butylbis(dimethylamino)antimony.

[0152] 11H-NMR (C6D6): δ 2.78 (s, 12H), δ 1.19 (s, 9H)

[0153] [Production Example 2] Production of Isopropylbis(dimethylamino)antimony

[0154]

[0155] In the above Production Example 1, 186 ml (0.13 mol) of isopropyllithium (0.7 M pentane solution) was used instead of tert-butylmagnesium chloride, and otherwise, the same procedure was carried out to obtain 14 g of isopropylbis(dimethylamino)antimony.

[0156] 1 1H NMR (C6D6): δ 2.85 (s, 12H), δ 1.80 (st, 1H) δ 1.18 (d, 6H)

[0157] Figure 1 The TGA analysis results of the tert-butylbis(dimethylamino)antimony produced in Production Example 1 are shown. Referring to Figure 1 , it can be seen that the antimony compound of Production Example 1 has a single evaporation step at about 120 °C, and it is confirmed that the residue mass at 500 °C is 0.9%, showing a rapid gasification characteristic, and it can be seen that more than 99% is gasified without thermal decomposition. Based on such results, it can be known that the thermal stability of the antimony compound of Production Example 1 is very excellent.

[0158] Figure 2 These are the results of measuring the vapor pressure to confirm the vapor pressure characteristics of the tert-butylbis(dimethylamino)antimony produced in Production Example 1.

[0159] Figure 3 The TGA analysis results of the isopropylbis(dimethylamino)antimony produced in Production Example 2 are shown. Referring to Figure 3 , it can be seen that the antimony compound of Production Example 2 has a single evaporation step at about 95 °C, and it is confirmed that the residue mass at 500 °C is 0.2%, showing a rapid gasification characteristic, and it can be seen that more than 99% is gasified without thermal decomposition. Based on such results, it can be known that the thermal stability of the antimony compound of Production Example 2 is very excellent.

[0160] Figure 4 These are the results of measuring the vapor pressure to confirm the vapor pressure characteristics of the isopropylbis(dimethylamino)antimony produced in Production Example 2.

[0161] [Example 1]

[0162] A plasma enhanced atomic layer deposition method is used to fabricate an antimony-containing thin film. As precursors, tert-butylbis(dimethylamino)antimony fabricated in Production Example 1 and isopropylbis(dimethylamino)antimony fabricated in Production Example 2 are respectively used, and oxygen is used as the reaction gas.

[0163] A silicon substrate is used as the substrate on which the antimony-containing thin film is to be formed. The silicon substrate is transferred into the evaporation chamber and constantly maintained at the temperature recorded in Table 1 below.

[0164] A stainless-steel bubbler type vial filled with the precursor is maintained at a temperature that achieves the constant precursor vapor pressure recorded in Table 1. The vaporized precursor is transferred into the chamber using argon as the transfer gas and adsorbed onto the silicon substrate. Then, a purging process is carried out using argon. A reaction process is carried out using oxygen as the reaction gas at the constant plasma power recorded in Table 1 below. In addition, a purging process is carried out using argon to remove reaction by-products. The atomic layer deposition process described above is regarded as one cycle, and a certain number of cycles are repeated to form the antimony-containing thin film. The detailed evaluation conditions and results are shown in Table 1.

[0165] In addition, the composition of the antimony-containing thin film is analyzed by X-ray photoelectron spectroscopy. Since no carbon and nitrogen are detected, it is confirmed that a pure antimony-containing thin film can be obtained.

[0166] [Table 1]

[0167]

[0168] [Example 2]

[0169] An atomic layer deposition method is used to fabricate an antimony-containing thin film. As precursors, tert-butylbis(dimethylamino)antimony fabricated in Production Example 1 and isopropylbis(dimethylamino)antimony fabricated in Production Example 2 are respectively used, and ozone gas is used as the reaction gas.

[0170] A silicon substrate is used as the substrate on which the antimony-containing thin film is to be formed. The silicon substrate is transferred into the evaporation chamber and maintained at the constant temperature recorded in Table 2 below.

[0171] A bubbler-type small pot made of stainless steel filled with a precursor is maintained at a temperature that achieves a constant precursor vapor pressure as described in Table 2 below. The vaporized precursor is transferred into the chamber using argon as a transfer gas and adsorbed onto a silicon substrate. Then, a purification process is carried out using argon, and a reaction process is carried out using ozone gas as a reaction gas. In addition, a purification process is carried out using argon to remove reaction by-products. The atomic layer deposition process described above is taken as one cycle, and a certain number of cycles are repeated to form an antimony-containing film. The detailed evaluation conditions and results are shown in Table 2.

[0172] In addition, the composition of the antimony-containing film was analyzed by X-ray photoelectron spectroscopy. Since no carbon and nitrogen were detected, it was confirmed that a pure antimony-containing film could be obtained.

[0173] [Table 2]

[0174]

[0175] [Example 3]

[0176] An antimony-containing film was fabricated using plasma-enhanced atomic layer deposition (PEALD). As precursors, tert-butylbis(dimethylamino)antimony fabricated in Production Example 1 and isopropylbis(dimethylamino)antimony fabricated in Production Example 2 were used respectively, and carbon dioxide gas was used as the reaction gas.

[0177] The substrate on which the antimony-containing film was to be formed was a silicon substrate, which was transferred into the deposition chamber and maintained at a constant temperature as described in Table 3 below.

[0178] A bubbler-type small pot made of stainless steel filled with a precursor is maintained at a temperature that achieves a constant precursor vapor pressure as described in Table 3 below. The vaporized precursor is transferred into the chamber using argon as a transfer gas and adsorbed onto a silicon substrate. Then, a purification process is carried out using argon. The reaction process is carried out using carbon dioxide gas as the reaction gas at a constant plasma power as described in Table 3 below. In addition, a purification process is carried out using argon to remove reaction by-products. The atomic layer deposition process described above is taken as one cycle, and a certain number of cycles are repeated to form an antimony-containing film. The detailed evaluation conditions and results are shown in Table 3.

[0179] In addition, the composition of the antimony-containing film was analyzed by X-ray photoelectron spectroscopy and was confirmed to be a film containing 10% or more carbon.

[0180] [Table 3]

[0181]

[0182]

[0183] [Example 4]

[0184] A thin film containing antimony was fabricated using chemical vapor deposition (CVD). As precursors, tert-butylbis(dimethylamino)antimony fabricated in Production Example 1 and isopropylbis(dimethylamino)antimony fabricated in Production Example 2 were used respectively, and water vapor was used as the reaction gas.

[0185] A silicon substrate on which a thin film containing antimony was to be formed was transferred into a vapor deposition chamber and maintained at a constant temperature shown in Table 4 below.

[0186] A stainless-steel bubbler-type vial filled with the precursor was maintained at a temperature at which the precursor vapor pressure reached a constant value shown in Table 4 below. The vaporized precursor was transferred into the chamber using argon as a carrier gas. In addition, for water vapor as the reaction gas, a stainless-steel bubbler-type vial filled with water was maintained at a temperature at which the vapor pressure reached a constant value shown in Table 4 below, and transferred into the chamber using argon as a carrier gas. Further, the process pressure was adjusted using a throttle valve to maintain the chamber pressure constantly. Thus, a thin film containing antimony was formed by performing chemical vapor deposition using the above precursor and water vapor. Detailed evaluation conditions and results are shown in Table 4.

[0187] In addition, the composition of the thin film containing antimony was analyzed by X-ray photoelectron spectroscopy, and it was confirmed that the thin film contained 10% or more carbon.

[0188] [Table 4]

[0189]

[0190]

[0191] <Patterning of the Antimony-Containing Thin Film>

[0192] [Example 5]

[0193] Patterning of the antimony-containing thin film fabricated in Example 3 was carried out.

[0194] In order to form 1:1 line-space features at a pitch of 24 nm, a pattern was formed using EUV exposure at approximately 76 mJ / cm 2 Then, firing was carried out at 150 degrees for 3 minutes, development was carried out in 2-heptanone for approximately 15 seconds, and then rinsing was carried out using the same solvent.

[0195] Figure 5It is an image of a scanning electron microscope of a line / space pattern formed on a silicon substrate with a pitch of 24 nm. Figure 5 (a) of Figure 5 is an image of the pattern using tert-butylbis(dimethylamino)antimony of Production Example 1, and (b) is an image of the pattern using isopropylbis(dimethylamino)antimony of Production Example 2.

[0196] As shown in the image of the pattern, it can be confirmed that a 1:1 line / space pattern was uniformly formed even at a narrow pitch of 24 nm.

Claims

1. A composition for vapor deposition of an antimony-containing thin film, which comprises an antimony compound represented by the following Chemical Formula 1: Chemical Formula 1 In the Chemical Formula 1, R1 to R5 are each independently a linear or branched C1-C7 alkyl group.

2. The composition for vapor deposition of an antimony-containing thin film according to claim 1, wherein in the Chemical Formula 1, R1 to R4 are each independently a linear C1-C7 alkyl group, and R5 is a branched C3-C7 alkyl group.

3. The composition for vapor deposition of an antimony-containing thin film according to claim 1, wherein the antimony compound represented by the Chemical Formula 1 is represented by the following Chemical Formula 2: Chemical Formula 2 In the Chemical Formula 2, R 11 and R 12 each independently is a linear or branched C1-C7 alkyl group; R5 is a branched C3-C7 alkyl group.

4. The composition for vapor deposition of an antimony-containing thin film according to claim 3, wherein R5 is a branched C3-C5 alkyl group.

5. The composition for vapor deposition of an antimony-containing thin film according to claim 1, wherein the antimony compound is selected from the following compounds, 6. A method for manufacturing an antimony-containing thin film, which uses the composition for vapor deposition of an antimony-containing thin film according to any one of claims 1 to 5.

7. The method for manufacturing an antimony-containing thin film according to claim 6, wherein the manufacturing method includes: a) a step of maintaining the temperature of a substrate installed in a chamber at 30 to 500 °C; b) a step of bringing the composition for vapor deposition of an antimony-containing thin film according to any one of claims 1 to 5 into contact with the substrate to adsorb it onto the substrate; and c) a step of injecting a reaction gas into the substrate adsorbed with the composition for vapor deposition of an antimony-containing thin film to form an antimony-containing thin film.

8. The method for manufacturing an antimony-containing thin film according to claim 7, wherein the reaction gas contains 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 a combination thereof.

9. The method for manufacturing an antimony-containing thin film according to claim 7, wherein the reaction gas is supplied after generating and activating a plasma of 50 to 1,000 W.

10. An antimony compound, which is represented by the following Chemical Formula 1: Chemical Formula 1 In the Chemical Formula 1, R1 to R4 are each independently a linear or branched C1-C7 alkyl group; and R5 is a branched C1-C7 alkyl group.

11. The antimony compound according to claim 10, wherein the antimony compound is represented by the following Chemical Formula 2: Chemical Formula 2 In the Chemical Formula 2, R 11 and R 12 each independently is a linear or branched C1-C7 alkyl group; R5 is a branched C3-C7 alkyl group.

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