Composition for depositing antimony-containing thin film and method for manufacturing antimony-containing thin film by using same

Abstract

The present invention relates to a composition for depositing an antimony-containing thin film and a method for manufacturing an antimony-containing thin film by using the same, the composition comprising an antimony compound which can be effectively used as a precursor of an antimony-containing thin film. The antimony compound according to one embodiment is in a liquid state at room temperature, and thus has excellent storability and handling properties and high reactivity, thereby being capable of effectively forming a metal thin film.

Description

Technical Field

[0001] The present invention relates to compositions for depositing antimony-containing thin films and methods for manufacturing antimony-containing thin films using the same, wherein the compositions for depositing antimony-containing thin films contain novel antimony compounds as precursors for the antimony-containing thin films. Background Technology

[0002] Antimony-containing (Sb) thin films, due to their excellent thin film properties, can be used as insulating layers, anti-diffusion layers, hard masks, etch stop layers, seed layers, spacers, intermetallic dielectric materials, protective films, anti-reflective layers, and more, with increasingly diversified applications. In particular, antimony-containing thin films exhibit excellent etch resistance and are attracting considerable attention as a next-generation material for hard masks in EUV lithography processes.

[0003] Meanwhile, semiconductor circuits are becoming increasingly miniaturized year by year due to their high performance. This miniaturization, increased aspect ratio, and diversification of device materials necessitate the development of ultrafine films with uniform and small thicknesses, excellent electrical properties, and etch resistance, even at low temperatures. However, conventional antimony-containing thin film precursors involve high-temperature processes, making their application to plastic substrates difficult. Lowering the process temperature may result in reduced film deposition rates and purity, as well as limitations in step coverage, etch resistance, and physical and electrical properties. Summary of the Invention Technical issues

[0004] One object of the present invention is to provide a composition for depositing antimony-containing thin films, which can provide antimony-containing thin films with excellent quality.

[0005] Another object of the present invention is to provide a method for manufacturing antimony-containing thin films, which allows for the deposition of thin films at high film deposition rates even under mild reaction conditions, and can produce high-quality antimony-containing thin films with high purity.

[0006] Another object of the present invention is to provide an antimony compound with a novel structure that can be used as a precursor for antimony-containing thin films. Technical solution

[0007] In one general aspect, the composition for depositing antimony-containing thin films, which allows for the manufacture of antimony-containing thin films with excellent quality, comprises: an antimony compound represented by the following chemical formula 1:

[0008] [Chemical Formula 1]

[0009]

[0010] Where R 1 It is a C1 to C7 alkyl group; R 2It is a C1 to C7 alkyl or C1 to C7 alkoxy; and A is a halogen or a C1 to C7 alkoxy.

[0011] Preferably, in chemical formula 1, R 1 It can be a C1 to C5 alkyl group; R 2 It can be a C1 to C5 alkyl or a C1 to C5 alkoxy; and A is a halogen or a C1 to C5 alkoxy.

[0012] Preferably, the antimony compound represented by chemical formula 1 can be represented by chemical formula 2 or chemical formula 3:

[0013] [Chemical Formula 2]

[0014]

[0015] [Chemical Formula 3]

[0016]

[0017] Where R 1 It is a C1 to C5 alkyl group; R 3 and R 4 Each of the following is independently a C1 to C5 alkyl or C1 to C5 alkoxy; R 5 It is a C1-C5 alkyl group; and X is a halogen.

[0018] According to one embodiment, the antimony compound may be selected from, but is not limited to, the following compounds:

[0019]

[0020]

[0021]

[0022] Where Me is methyl, Et is ethyl, and Pr is n-propyl or isopropyl.

[0023] In another general aspect, a method for manufacturing an antimony-containing thin film using the above-described composition for depositing an antimony-containing thin film is provided.

[0024] A method for manufacturing an antimony-containing thin film according to one embodiment of the present invention may include:

[0025] a) Maintain the temperature of the substrate installed in the room between 30°C and 500°C; and

[0026] b) Injecting the composition for depositing an antimony-containing thin film according to one embodiment of the present invention and the reactive gas into the substrate to form an antimony-containing thin film.

[0027] The reactant gases 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), anhydrous acetic acid ((CH3CO)2O), or combinations thereof.

[0028] The reactive gas can be supplied after activation by generating plasma at 20 W to 1,000 W.

[0029] In another general aspect, new compounds are provided that can be used as precursors for antimony-containing thin films of excellent quality, and these compounds can be antimony compounds represented by the following chemical formula 1:

[0030] [Chemical Formula 1]

[0031]

[0032] Where R 1 It is a C1 to C7 alkyl group; R 2 It is a C1 to C7 alkyl or C1 to C7 alkoxy; and A is a halogen or C1 to C7 alkoxy; but R is excluded. 1 For tert-butyl and R 2 The case where both A and B are ethoxylated.

[0033] More preferably, the antimony compound according to one embodiment can be represented by the following chemical formula 2 or chemical formula 3:

[0034] [Chemical Formula 2]

[0035]

[0036] [Chemical Formula 3]

[0037]

[0038] Where R 1 It is a C1 to C5 alkyl group; R 3 and R 4 Each of the following is independently a C1 to C5 alkyl or C1 to C5 alkoxy; R 5 It is a C1 to C5 alkyl group; and X is I; but R is excluded. 1 For tert-butyl, R 4 For ethoxy and R 5 In the case of ethyl groups. Beneficial effects

[0039] The composition for depositing antimony-containing thin films according to one embodiment of the present invention is easy to store and handle, allows for the deposition of thin films at high film deposition rates even at low temperatures, and allows for the manufacture of antimony-containing thin films with excellent quality at high purity.

[0040] Furthermore, the composition for depositing antimony-containing thin films according to one embodiment of the present invention allows for the production of thin films with excellent quality in high yield, and thus can be usefully applied in various industrial fields.

[0041] In particular, the antimony compounds of the present invention have excellent light absorption and luminescence effects for EUV, and therefore can be very useful as hard masks, etc., used in EUV lithography processes. Attached Figure Description

[0042] Figure 1 The TGA analysis results of the bis(tert-butyl)antimony iodide prepared in Example 1 are shown.

[0043] Figure 2 The TGA analysis results are shown for the antimony bis(tert-butyl)ethoxy prepared in Example 2.

[0044] Figure 3 The TGA analysis results are shown for the (tert-butyl)bisethoxyantimony prepared in Example 3.

[0045] Figure 4 The results are from scanning electron microscopy (SEM) analysis of the line / spacing pattern formed in Example 8. Detailed Implementation Plan

[0046] The invention will now be described in detail to enable those skilled in the art to readily practice it. However, the invention can be embodied in various different forms and is not limited to the embodiments described herein. Furthermore, it is not intended to limit the scope of protection defined by the claims.

[0047] Furthermore, unless otherwise defined, the technical and scientific terms used in the description of this invention have the meanings commonly understood by those skilled in the art, and descriptions of known functions and configurations that obscure the invention will be omitted in the following description.

[0048] The numerical range used in this specification includes all values ​​within a range that includes both a lower and upper limit, increments logically derived in one form that cover the defined range, all double-limited values, and all possible combinations of upper and lower limits in numerical ranges defined in different forms. Unless otherwise defined in this specification, values ​​that may be outside the defined numerical range due to experimental error or rounding are also included within the defined numerical range.

[0049] Unless otherwise specifically defined in this invention, the word "comprising" any element shall be understood to imply the inclusion of other elements rather than the exclusion of any other elements. Furthermore, unless the context otherwise indicates, the singular forms used in the specification and appended claims may be intended to include the plural forms as well.

[0050] In this specification, the terms “CA to CB” mean “having A or more and B or fewer carbon atoms”, and the terms “A to B” mean “A or more and B or fewer carbon atoms”.

[0051] The term "alkyl" in this specification means a monovalent substituent and includes both linear and branched forms. Alkyl groups can have 1 to 7 carbon atoms, specifically 1 to 5 carbon atoms.

[0052] As examples, alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, etc.

[0053] In this specification, the term "alkoxy" means an -O-alkyl group, where "alkyl" is as defined above. Specific examples include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, etc.

[0054] The term "halogen" in this specification refers to a Group 17 element and can be any one selected from F, Cl, Br and I.

[0055] In this specification, "normal temperature" can refer to the temperature without any artificial temperature regulation, and for example, normal temperature can be 20°C to 40°C or 20°C to 30°C.

[0056] Furthermore, when specific manufacturing tolerances and material tolerances are indicated in the sense of reference, the term "about" in this specification is used in the sense of that numerical value or a value close to that value, and is intended to prevent unlawful use by malicious infringers of the disclosure of precise or absolute numerical values ​​for the purpose of better understanding this specification and the appended claims.

[0057] The present invention will be described in detail below.

[0058] A composition for depositing antimony-containing thin films according to one embodiment of the present invention comprises a precursor compound having a specific structure and can provide high-quality antimony-containing thin films.

[0059] Specifically, according to one embodiment, the precursor compound can be an antimony compound represented by the following chemical formula 1:

[0060] [Chemical Formula 1]

[0061]

[0062] in

[0063] R 1 It is a C1 to C7 alkyl group; R 2 It is a C1 to C7 alkyl or C1 to C7 alkoxy; and A is a halogen or a C1 to C7 alkoxy.

[0064] Unbound by any particular theory, antimony compounds represented by Formula 1 exist in a liquid state at room temperature and can exhibit excellent reactivity and volatility. Therefore, a composition for depositing antimony-containing thin films according to one embodiment of the present invention is easy to store and handle, allows for high film deposition rates even at low temperatures, and can provide antimony-containing thin films with high purity and excellent durability.

[0065] Furthermore, antimony-containing films manufactured from a composition for depositing antimony-containing films according to one embodiment are highly advantageous for forming feature size patterns compared to currently used chemically amplified resists (CARs). CARs have high sensitivity, but the O, F, S, and C elements typically composed of these elements make the photoresist too transparent at certain wavelengths, thus reducing sensitivity.

[0066] Furthermore, chemically amplified resists (CARs) can be difficult to pattern due to roughness issues in small feature sizes, and line edge roughness (LER) increases as the light velocity decreases, partly due to the nature of the acid-catalyzed process. However, antimony compounds according to an exemplary embodiment of the invention exhibit excellent light absorption and luminescence effects for EUV, and are therefore very useful as hard masks for use in EUV lithography processes.

[0067] Specifically, in chemical formula 1 according to an exemplary embodiment of the present invention, R 1 It can be a C1 to C7 alkyl group;

[0068] R 2 The alkyl group can be C1 to C7 alkyl or C1 to C7 alkoxy; and A can be a halogen or a C1 to C7 alkoxy. For example, the C1 to C7 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. Preferably, it can be a branched alkyl group, and more preferably, it can be isopropyl, isobutyl, or tert-butyl. Furthermore, the C1 to C7 alkoxy group can be methoxy, ethoxy, propoxy, or butoxy, and preferably can be C1 to C3 alkoxy, and specifically methoxy or ethoxy. The halogen can be any of F, Cl, Br, and I, and can preferably be I.

[0069] Furthermore, in chemical formula 1 according to an exemplary embodiment of the present invention, R 1 It can be a C1 to C5 alkyl group; R 2 It can be a C1 to C5 alkyl or a C1 to C5 alkoxy; and A can be a halogen or a C1 to C5 alkoxy.

[0070] As an example, antimony compounds represented by chemical formula 1 can be represented by the following chemical formula 2 or chemical formula 3:

[0071] [Chemical Formula 2]

[0072]

[0073] [Chemical Formula 3]

[0074]

[0075] Where R 1 It is a C1 to C5 alkyl group; R 3 and R 4 Each of the following is independently a C1 to C5 alkyl or C1 to C5 alkoxy; R 5 It is a C1 to C5 alkyl group; and X is a halogen.

[0076] Specifically, in Formulas 2 and 3, the C1 to C5 alkyl groups can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. Preferably, they can be branched alkyl groups, and more preferably, they can be isopropyl, isobutyl, or tert-butyl. Furthermore, the C1 to C7 alkoxy groups can be methoxy, ethoxy, propoxy, or butoxy, and preferably C1 to C3 alkoxy groups, specifically methoxy or ethoxy. The halogen can be any of F, Cl, Br, and I, and is preferably I.

[0077] Antimony compounds represented by chemical formula 1 may be selected, for example, from, but not limited to, the following compounds:

[0078]

[0079]

[0080]

[0081] Where Me is methyl, Et is ethyl, and Pr is n-propyl or isopropyl.

[0082] According to one embodiment, the composition for depositing antimony-containing thin films must contain an antimony compound represented by Formula 1 as a precursor for film deposition, and the content of the compound represented by Formula 1 in the composition is within a range that can be identified by those skilled in the art considering the film formation conditions, film thickness, film properties, and intended use of the film. Furthermore, another embodiment of the invention provides a method for manufacturing antimony-containing thin films using the aforementioned composition for depositing antimony-containing thin films.

[0083] A method for manufacturing antimony-containing thin films according to one embodiment allows for the production of high-quality antimony-containing thin films at high deposition rates, even at low temperatures and low power, due to the use of a composition comprising an antimony compound represented by Chemical Formula 1 as a precursor. Antimony-containing thin films can be used for various purposes, such as insulating films, anti-diffusion films, hard masks, etch stop layers, seed layers, spacers, antireflective layers, intermetallic dielectric materials, and protective film layers in electronic device manufacturing, and are preferably used as hard masks in EUV lithography processes, but are not limited thereto.

[0084] In a method for manufacturing an antimony-containing thin film according to one embodiment, the method used for depositing the thin film is not particularly limited, as long as it is commonly used in the art. However, 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) can be used. Specifically, ALD, CVD, or PEALD can be used, but the invention is not limited thereto.

[0085] A method for manufacturing an antimony-containing thin film according to one embodiment may include:

[0086] a) Maintain the temperature of the substrate installed in the room between 30°C and 500°C; and

[0087] b) Injecting the composition for depositing an antimony-containing thin film according to one embodiment of the present invention and the reactive gas into the substrate to form an antimony-containing thin film.

[0088] A method for manufacturing an antimony-containing thin film according to one embodiment may further include purging residual deposited components, reactive gases, and byproducts.

[0089] While there are no particular limitations on the substrate, it may be any substrate commonly used in the art, such as a substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a silicon-on-insulator (SOI) substrate; a quartz substrate; 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), and polyester.

[0090] In addition, antimony-containing thin films can be formed directly on the substrate, but multiple conductive layers, dielectric layers, insulating layers, etc. can also be further formed between the substrate and the antimony-containing thin film.

[0091] As an example, the temperature of the substrate can be 30°C to 500°C, 30°C to 300°C, or 50°C to 300°C, but is not limited to these.

[0092] As an example, the reactive gas can be supplied after activation by generating plasma at 20 W to 1,000 W, 20 W to 800 W, or 50 W to 600 W.

[0093] Specifically, in a method for manufacturing antimony-containing thin films according to one embodiment, the thin films can be efficiently manufactured even at low temperatures and in the presence of low plasma generation by using a compound of chemical formula 1 as a precursor.

[0094] The reactive gas can remove ligands of antimony compounds contained in the composition used to deposit antimony-containing thin films to form an antimony-containing atomic layer.

[0095] There are no particular restrictions on the type of reactant gas, as long as it is commonly used in the art. However, as examples, 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), anhydrous acetic acid ((CH3CO)2O), or combinations thereof.

[0096] As an example, the concentration of ozone in the reaction gas can be 10 g / m³. 3 Up to 220 g / m 3 However, it is not limited to this.

[0097] In a method for manufacturing an antimony-containing thin film according to one embodiment, an inert gas can be used as the transfer gas or purge gas. There are no particular limitations on the type of transfer gas or purge gas, as long as it is commonly used in the art; however, examples include argon, nitrogen, krypton, etc., and argon is preferred because it is economical.

[0098] In a method for manufacturing an antimony-containing thin film according to one embodiment, deposition conditions can be adjusted according to the desired structure or thermal properties of the film. The deposition conditions according to one embodiment can be, for example, the input flow rate of the composition for depositing the antimony-containing thin film containing a compound of Formula 1, the input flow rate of the reactant gas and the transfer gas, the pressure, the RF power, the substrate temperature, etc. As a non-limiting example, the input flow rate of the composition for depositing the antimony-containing thin film can be from 10 cc / min to 1000 cc / min, the transfer gas can be from 10 cc / min to 1000 cc / min, the reactant gas flow rate can be from 1 cc / min to 1500 cc / min, the pressure can be from 0.5 Torr to 10 Torr, and the RF power and substrate temperature can be as described above.

[0099] Furthermore, another embodiment of the present invention provides a novel compound that can be used as a precursor for antimony-containing thin films. Specifically, the novel compound can be an antimony compound represented by the following chemical formula 1:

[0100] [Chemical Formula 1]

[0101]

[0102] Where R 1 It is a C1 to C7 alkyl group; R 2 The C1 to C7 alkyl or C1 to C7 alkoxy group is a C1 to C7 alkyl group; and A is a halogen or a C1 to C7 alkoxy group. Specifically, in Formula 1, the C1 to C7 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, or neopentyl. Preferably, it can be a branched C3 to C5 alkyl group, and more preferably tert-butyl. Furthermore, the C1 to C7 alkoxy group can be methoxy, ethoxy, propoxy, or butoxy, and can preferably be ethoxy. The halogen can be any of F, Cl, Br, and I, and can preferably be I. However, R is excluded. 1 For tert-butyl and R 2 The case where both A and B are ethoxylated.

[0103] Antimony compounds represented by chemical formula 1 can, for example, be represented by chemical formula 2 or chemical formula 3:

[0104] [Chemical Formula 2]

[0105]

[0106] [Chemical Formula 3]

[0107]

[0108] Where R 1 It is a C1 to C5 alkyl group; R 3 and R 4 Each of the following is independently a C1 to C5 alkyl or C1 to C5 alkoxy; R 5 It is a C1 to C5 alkyl group; and X is I.

[0109] However, excluding R 1 For tert-butyl, R 4 For ethoxy and R 5 In the case of ethyl groups.

[0110] The antimony compound according to one embodiment of the present invention can be prepared using any method feasible to those skilled in the art.

[0111] The exemplary embodiments described above will be described in detail below through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of the claims.

[0112] The physical characteristics of the embodiments are measured as follows:

[0113] 1) Elemental composition analysis

[0114] The elemental composition of the thin film was analyzed using X-ray photoelectron spectroscopy (K-α+, ThermoFisher Scientific).

[0115] 2) Thermogravimetric analysis

[0116] Thermogravimetric analysis (TGA, L81-II, LINSEIS) was performed by heating the sample to be analyzed to 500°C at a rate of 10°C / min while injecting nitrogen gas at a pressure of 1.5 bar / min.

[0117] [Example 1] Preparation of bis(tert-butyl)antimony iodide

[0118]

[0119] 120 g (0.53 mol) antimony trichloride (SbCl3) was added to a 10 L flask, followed by 3,000 mL of diethyl ether, and the mixture was stirred while maintaining the internal temperature at 10 °C. 526 mL (1.06 mol) of tert-butylmagnesium chloride (a 2.0 M solution in diethyl ether) was slowly added to the flask while maintaining the internal temperature at 10 °C, and the mixture was stirred at room temperature for 4 hours. After the reaction was complete, the residue was removed through a filter, and the solvent and byproducts were removed under reduced pressure. Subsequently, purification was carried out at 42 °C and 0.4 Torr to synthesize 70 g of bis(tert-butyl)antimony chloride.

[0120]

[0121] 16.7 g (0.11 mol) of NaI was added to a 1 L flask, followed by 300 mL of hexane. The mixture was stirred while maintaining the internal temperature at 20 °C. 30 g (0.11 mol) of the prepared bis(tert-butyl)antimony chloride (Sb(t-Butyl)₂Cl) was added to the flask, and the mixture was stirred at room temperature for 4 hours to synthesize bis(tert-butyl)antimony iodide. After the reaction was complete, the residue was removed through a filter, and the solvent and byproducts were removed under reduced pressure to obtain bis(tert-butyl)antimony iodide. Subsequently, purification was carried out at 44 °C and 0.24 Torr to obtain 30 g of bis(tert-butyl)antimony iodide.

[0122]

[0123] The TGA analysis results of the bis(tert-butyl)antimony iodide prepared in Example 1 are shown in... Figure 1 Furthermore, it was found that the antimony compound of Example 1 exhibited a single evaporation step from approximately 140°C, and the residue mass at 500°C was confirmed to be 23.0%, indicating that the compound was evaporated and exhibited rapid evaporation characteristics. The results suggest that the antimony compound of Example 1 possesses excellent thermal stability.

[0124] [Example 2] Preparation of bis(tert-butyl)ethoxyantimony

[0125]

[0126] 5.52 g (0.08 mol) of NaOEt was added to a 500 mL flask, followed by 100 mL of ethanol. The mixture was stirred while maintaining the internal temperature at 20 °C. 22 g (0.08 mol) of the prepared bis(tert-butyl)antimony chloride (Sb(t-Butyl)₂Cl) was added to the flask, and the mixture was stirred at room temperature for 4 hours to synthesize bis(tert-butyl)ethoxyantimony. After the reaction was complete, the residue was removed through a filter, and the solvent and byproducts were removed under reduced pressure to obtain bis(tert-butyl)ethoxyantimony (13 g). Subsequently, purification was carried out at 22 °C and 0.41 Torr to obtain 8 g of bis(tert-butyl)ethoxyantimony.

[0127]

[0128] The TGA analysis results of the bis(tert-butyl)ethoxyantimony prepared in Example 2 are shown in... Figure 2 Furthermore, it was found that the antimony compound of Example 2 exhibited a single evaporation step from approximately 70°C, and the residue mass at 500°C was confirmed to be 2.9%, indicating that the compound was evaporated and exhibited rapid evaporation characteristics. The results suggest that the antimony compound of Example 2 possesses excellent thermal stability.

[0129] [Example 3] Preparation of tert-butyldiethoxyantimony

[0130]

[0131] 169 mL (0.41 mol) of n-butyllithium (2.3 M solution in n-hexane) was added to a 500 mL flask, followed by 300 mL of n-hexane and stirring. 19 g (0.41 mol) of dimethylamine was slowly added while maintaining the internal temperature of the mixture at -10 °C, and the mixture was then stirred at room temperature (25 °C) for 2 hours to synthesize (dimethylamine)lithium.

[0132] 30 g (0.13 mol) of antimony trichloride (SbCl3) was added to a 1 L flask, followed by 300 mL of diethyl ether. The mixture was stirred while maintaining the internal temperature at -10 °C. 21 g of the prepared (dimethylamine)lithium was slowly added to the flask, and the mixture was stirred at room temperature for 4 hours to synthesize tribis(methylamine)antimony. After synthesis, lithium chloride (LiCl) was removed through a filter, the solvent was removed under vacuum, 300 mL of hexane was added, and the mixture was stirred while maintaining the internal temperature at -20 °C.

[0133] While maintaining the internal temperature at -20°C, 65 ml (0.13 mol) of tert-butylmagnesium chloride (2.0 M solution in diethyl ether) was slowly added to the flask, and the mixture was stirred at room temperature for 4 hours. After the reaction was complete, the solvent and byproducts were removed under reduced pressure. Subsequently, purification was carried out at 30°C and 0.4 Torr to synthesize 15 g of tert-butylbis(dimethylamino)antimony.

[0134]

[0135] 15.0 g (0.06 mol) of tert-butylbis(dimethylamino)antimony was added to a 500 mL flask, followed by 60 mL of hexane, and the mixture was stirred thoroughly. While maintaining the internal temperature of the solution at -40 °C, 5.18 g (0.12 mol) of ethanol was slowly added, and the mixture was stirred at room temperature for 4 hours to synthesize tert-butylbisethoxyantimony. After the reaction was complete, the residue was removed through a filter, and the solvent and byproducts were removed under reduced pressure to obtain 12 g of tert-butylbisethoxyantimony.

[0136] Subsequently, purification was carried out at 16°C and 0.49 Torr to obtain 10 g of tert-butylbisethoxyantimony.

[0137]

[0138] The TGA analysis results of the tert-butylbisethoxyantimony prepared in Example 3 are shown in... Figure 3 Furthermore, it was found that the antimony compound of Example 3 exhibited a single evaporation step from approximately 100°C, and the residue mass at 500°C was confirmed to be 5.0%, indicating that the compound was evaporated and exhibited rapid evaporation characteristics. The results suggest that the antimony compound of Example 3 possesses excellent thermal stability.

[0139] [Example 4]

[0140] Using the antimony bis(tert-butyl)iodide, antimony bis(tert-butyl)ethoxy and antimony tert-butyldiethoxy as antimony precursors, antimony oxide thin films were fabricated by plasma-enhanced atomic layer deposition.

[0141] A silicon substrate is used as the substrate on which an antimony oxide film is to be formed, and the silicon substrate is transferred to a deposition chamber in which the temperature is maintained at a certain temperature.

[0142] The temperature of the stainless steel container holding the antimony precursor was maintained to ensure a constant vapor pressure. The vaporized antimony precursor was transferred to the chamber using argon as the transfer gas and adsorbed onto the silicon substrate. A purging process was then performed using argon. Oxygen was used as the reactant gas, and the reaction process was carried out using a constant plasma power. Furthermore, a purging process using argon was performed to remove reaction byproducts. The atomic layer deposition process described above was configured as a cycle, and this specific cycle was repeated to form an antimony oxide film. Detailed deposition conditions are shown in Table 1 below.

[0143] The composition of antimony oxide films deposited under specific conditions as shown in Table 1 for each precursor was analyzed by X-ray photoelectron spectroscopy, and it was determined that pure antimony oxide films could be obtained since no carbon or iodine was detected.

[0144] [Table 1]

[0145]

[0146] [Example 5]

[0147] Using the antimony bis(tert-butyl)iodide, antimony bis(tert-butyl)ethoxy and antimony tert-butyldiethoxy as antimony precursors, antimony oxide thin films were fabricated by atomic layer deposition.

[0148] A silicon substrate is used as the substrate on which an antimony oxide film is to be formed, and the silicon substrate is transferred to a deposition chamber in which the temperature is maintained at a certain temperature.

[0149] The temperature of the stainless steel container holding the antimony precursor was maintained to ensure a constant vapor pressure. Argon was used as the transfer gas to transfer the vaporized antimony precursor into the chamber, where it was adsorbed onto the silicon substrate. A purging process was then performed using argon. Ozone gas of a specific concentration was used as the reaction gas for the reaction process. Furthermore, an argon purging process was used to remove reaction byproducts. The atomic layer deposition process described above was set as a cycle, and this specific cycle was repeated to form an antimony oxide film. Detailed deposition conditions are shown in Table 2 below.

[0150] The composition of antimony oxide films deposited under specific conditions as shown in Table 2 for each precursor was analyzed by X-ray photoelectron spectroscopy, and it was determined that pure antimony oxide films could be obtained since no carbon or iodine was detected.

[0151] [Table 2]

[0152]

[0153] [Example 6]

[0154] Using the antimony bis(tert-butyl)iodide, antimony bis(tert-butyl)ethoxy and antimony tert-butyldiethoxy as antimony precursors, antimony-containing thin films were fabricated by plasma-enhanced atomic layer deposition.

[0155] A silicon substrate is used as the substrate on which an antimony-containing thin film is to be formed, and the silicon substrate is transferred to a deposition chamber in which the temperature is maintained at a certain temperature.

[0156] The temperature of the stainless steel container holding the antimony precursor was maintained to ensure a constant vapor pressure. Argon was used as the transfer gas to transfer the vaporized antimony precursor into the chamber, where it was adsorbed onto the silicon substrate. A purging process was then performed using argon. Carbon dioxide was used as the reactant gas, and the reaction process was conducted with a constant plasma power. Furthermore, an argon purging process was used to remove reaction byproducts. The atomic layer deposition process described above was configured as a cycle, and this specific cycle was repeated to form an antimony-containing thin film. Detailed deposition conditions are shown in Table 3 below.

[0157] The composition of antimony oxide films deposited under specific conditions as shown in Table 3 was analyzed by X-ray photoelectron spectroscopy, and the results are shown in Table 4 below. It was determined that the films formed from bis(tert-butyl)antimony iodide contained carbon and iodine in addition to antimony, and the films formed from bis(tert-butyl)ethoxyantimony or tert-butyldiethoxyantimony contained carbon in addition to antimony.

[0158] [Table 3]

[0159]

[0160] [Table 4]

[0161]

[0162] [Example 7]

[0163] Using the bis(tert-butyl)antimony iodide, bis(tert-butyl)ethoxyantimony and tert-butylbisethoxyantimony prepared in Examples 1 to 3 as antimony precursors, antimony-containing thin films were fabricated by chemical vapor deposition.

[0164] A silicon substrate is used as the substrate on which an antimony-containing thin film is to be formed, and the silicon substrate is transferred to a deposition chamber in which the temperature is maintained at a certain temperature.

[0165] The temperature of the bubbling tank containing the antimony precursor was maintained to ensure a constant vapor pressure of the precursor. Argon was used as the transfer gas to transfer the vaporized antimony precursor into the chamber. Furthermore, water vapor was used as the reactant gas to maintain a constant vapor pressure in the stainless steel tank containing water, and argon was used as the transfer gas to transfer the water vapor into the chamber. The process pressure was adjusted to maintain a constant chamber pressure using a throttling valve. Thus, chemical vapor deposition was performed using the antimony precursor and water vapor to form an antimony-containing thin film, and the detailed deposition conditions are shown in Table 5 below.

[0166] The composition of antimony oxide films deposited under specific conditions as shown in Table 5 for each precursor was analyzed using X-ray photoelectron spectroscopy. It was determined that films formed from bis(tert-butyl)antimony iodide contained carbon and iodine in addition to antimony, and films formed from bis(tert-butyl)ethoxyantimony or tert-butyldiethoxyantimony contained carbon in addition to antimony.

[0167] [Table 5]

[0168]

[0169] [Example 8] Patterning of antimony-containing thin films

[0170] Using the antimony bis(tert-butyl)iodide, antimony bis(tert-butyl)ethoxy and antimony tert-butyldiethoxy as antimony precursors, antimony-containing films were formed in the same manner as in Example 6.

[0171] To form a 1:1 line-to-pitch feature with a pitch of 24 nm, an exposure of 70 mJ / cm was used in an EUV lithography device. 2 Up to 80 mJ / cm 2 Patterning was performed using EUV. Subsequently, the mixture was fired at 150°C for 3 minutes, developed in 2-heptanone for 15 seconds, and rinsed with the same solvent.

[0172] The results of scanning electron microscopy analysis of the 24 nm pitch line / spacing pattern formed on the silicon substrate are shown in... Figure 4 Furthermore, it was determined that a 1:1 line / spacing pattern was uniformly formed even at a narrow pitch of 24 nm.

Claims

1. A composition for depositing antimony-containing thin films, said composition comprising an antimony compound represented by the following chemical formula 1: [Chemical Formula 1] in R 1 It is a C1 to C7 alkyl group; R 2 It is a C1 to C7 alkyl or a C1 to C7 alkoxy; and A is a halogen or a C1 to C7 alkoxy group.

2. The composition for depositing antimony-containing thin films according to claim 1, Where R 1 It is a C1 to C5 alkyl group; R 2 It is a C1 to C5 alkyl or a C1 to C5 alkoxy; and A is a halogen or a C1 to C5 alkoxy group.

3. The composition for depositing antimony-containing thin films according to claim 1, wherein the antimony compound represented by chemical formula 1 is represented by chemical formula 2 or chemical formula 3: [Chemical Formula 2] [Chemical Formula 3] in R 1 It is a C1 to C5 alkyl group; R 3 and R 4 Each of them is independently a C1 to C5 alkyl or a C1 to C5 alkoxy; R 5 It is a C1 to C5 alkyl group; and X is a halogen.

4. The composition for depositing antimony-containing thin films according to claim 1, wherein the antimony compound is selected from the following compounds: Where Me is methyl, Et is ethyl, and Pr is n-propyl or isopropyl.

5. A method for manufacturing an antimony-containing thin film using the composition for depositing an antimony-containing thin film according to any one of claims 1 to 4.

6. The method for manufacturing an antimony-containing thin film according to claim 5, wherein the method comprises: a) Maintain the temperature of the substrate installed in the room between 30°C and 500°C; as well as b) Injecting the composition for depositing an antimony-containing thin film according to any one of claims 1 to 4 and the reactive gas into the substrate to form an antimony-containing thin film.

7. The method for manufacturing an antimony-containing thin film according to claim 6, wherein the reaction gas comprises 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), anhydrous acetic acid ((CH3CO)2O), or combinations thereof.

8. The method for manufacturing an antimony-containing thin film according to claim 6, wherein the reactive gas is supplied after activation by generating plasma at 20 W to 1,000 W.

9. An antimony compound represented by the following chemical formula 1: [Chemical Formula 1] in R 1 It is a C1 to C7 alkyl group; R 2 It is a C1 to C7 alkyl or a C1 to C7 alkoxy; and A is a halogen or a C1 to C7 alkoxy group; However, excluding R 1 For tert-butyl and R 2 The case where both A and B are ethoxylated.

10. The antimony compound according to claim 9, wherein the antimony compound is represented by chemical formula 2 or chemical formula 3: [Chemical Formula 2] [Chemical Formula 3] in R 1 It is a C1 to C5 alkyl group; R 3 and R 4 Each of them is independently a C1 to C5 alkyl or a C1 to C5 alkoxy; R 5 It is a C1 to C5 alkyl group; and X is I; However, excluding R 1 For tert-butyl, R 4 For ethoxy and R 5 In the case of ethyl groups.

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