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 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 an implementation is in a liquid state at room temperature, and thus has excellent storability and handling and has high reactivity, thereby enabling a metal thin film to be efficiently formed.

Description

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

[0001] The present invention relates to a composition for depositing an antimony-containing thin film comprising a novel antimony compound as a precursor of an antimony-containing thin film, and a method for producing an antimony-containing thin film using the same.

[0002] Antimony (Sb)-containing thin films exhibit excellent film properties and can be used as insulating films, diffusion barriers, hard masks, etch-stop layers, seed layers, spacers, intermetallic dielectric materials, protective films, and antireflection layers. Their applications are increasingly diverse. In particular, antimony-containing thin films exhibit excellent etching resistance and are attracting attention as a next-generation material for hard masks in EUV photolithography processes.

[0003] Meanwhile, semiconductor circuits are becoming increasingly miniaturized due to the advancement of high-performance devices. These miniaturizations, increased aspect ratios, and diversification of device materials necessitate the formation of ultra-fine thin films that possess superior electrical properties and etching resistance, while maintaining uniform thicknesses even at low temperatures. However, conventional precursors for antimony-containing thin films require high-temperature processes, making them difficult to apply to plastic substrates. Lowering the process temperature can lead to decreased film deposition rates and purity, and insufficient step coverage, etching resistance, and physical and electrical properties.

[0004] One aspect of the present invention provides a composition for depositing an antimony-containing thin film, which can provide an antimony-containing thin film of excellent quality.

[0005] In addition, one 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 manufactures a high-quality antimony-containing thin film with high purity.

[0006] In addition, one aspect of the present invention provides an antimony compound having a novel structure that can be usefully used as a precursor for an antimony-containing thin film.

[0007] The present invention provides an antimony-containing thin film deposition composition capable of producing an antimony-containing thin film of excellent quality, and the antimony-containing thin film deposition composition according to one aspect of the present invention may include an antimony compound represented by the following chemical formula 1.

[0008] [Chemical Formula 1]

[0009]

[0010] In the above chemical formula 1, R 1 is C1-C7 alkyl; R 2 is C1-C7 alkyl or C1-C7 alkoxy; A is halogen or C1-C7 alkoxy.

[0011] Preferably, R in the above chemical formula 1 1 is C1-C5 alkyl; R 2 is C1-C5 alkyl or C1-C5 alkoxy; A may be halogen or C1-C5 alkoxy.

[0012] Preferably, the antimony compound represented by the above chemical formula 1 may be represented by the following chemical formula 2 or 3.

[0013] [Chemical Formula 2]

[0014]

[0015] [Chemical Formula 3]

[0016]

[0017] In the above chemical formulas 2 and 3, R 1 is C1-C5 alkyl; R 3 and R 4 are independently C1-C5 alkyl or C1-C5 alkoxy; R 5 is C1-C5 alkyl; X is halogen.

[0018] The antimony compound according to one aspect may be selected from the compounds below, but is not limited thereto.

[0019]

[0020]

[0021]

[0022] (In the above structure, Me means methyl, Et means ethyl, and Pr means n-propyl or i-propyl.)

[0023] In addition, the present invention provides a method for manufacturing an antimony-containing thin film using the composition for depositing an antimony-containing thin film described above.

[0024] A method for manufacturing an antimony-containing thin film according to one aspect of the present invention is as follows:

[0025] a) A step of maintaining the temperature of a substrate mounted in a chamber at 30 to 500°C;

[0026] b) It may include a step of forming an antimony-containing thin film by injecting a composition for depositing an antimony-containing thin film according to one aspect of the present invention and a reaction gas onto a substrate.

[0027] The above reaction gas may include oxygen (O2), ozone (O3), oxygen plasma, hydrogen (H2), hydrogen plasma, water (H2O), hydrogen peroxide (H2O2), nitrogen (NO2), nitrogen monoxide (NO), nitrous oxide (N2O), ammonia (NH3), carbon dioxide (CO2), formic acid (HCOOH), acetic acid (CH3COOH), acetic anhydride ((CH3CO)2O), or a combination thereof.

[0028] The above reaction gas may be supplied after being activated by generating plasma of 20 to 1,000 W.

[0029] In addition, one aspect of the present invention provides a novel compound that can be used as a precursor of an antimony-containing thin film of excellent quality, wherein the compound may be an antimony compound represented by the following chemical formula 1.

[0030] [Chemical Formula 1]

[0031]

[0032] In the above chemical formula 1, R 1 is C1-C7 alkyl; R 2 is C1-C7 alkyl or C1-C7 alkoxy; A is halogen or C1-C7 alkoxy; provided that R 1 This is t-butyl and R 2 and A are both ethoxy.

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

[0034] [Chemical Formula 2]

[0035]

[0036] [Chemical Formula 3]

[0037]

[0038] In the above chemical formulas 2 and 3, R 1 is C1-C5 alkyl; R 3 and R 4 are independently C1-C5 alkyl or C1-C5 alkoxy; R 5 is C1-C5 alkyl; X is I; provided that the above R 1 This is t-butyl and R 4 This is ethoxy and R 5 Except for this ethyl case.

[0039] The composition for depositing an antimony-containing thin film according to one aspect of the present invention can be easily stored and handled, can deposit a thin film at a high thin film deposition rate even under low temperature conditions, and can produce an antimony-containing thin film of excellent quality with high purity.

[0040] In addition, the composition for depositing an antimony-containing thin film according to one aspect of the present invention can produce a thin film of excellent quality with a high yield, and thus can be usefully applied to various industrial fields.

[0041] In particular, the antimony compound of the present invention has excellent light absorption rate and light emission effect for EUV, and can be very usefully used as a hard mask used in an EUV photolithography process.

[0042] Figure 1 is a TGA analysis result spectrum of bis(t-butyl)iodoantimony manufactured in Example 1.

[0043] Figure 2 is a TGA analysis result spectrum of bis(t-butyl)ethoxyantimony manufactured in Example 2.

[0044] Figure 3 is a TGA analysis result spectrum of (t-butyl)bisethoxyantimony manufactured in Example 3.

[0045] Figure 4 is a scanning electron microscope (SEM) analysis result of the line / space pattern formed in Example 8.

[0046] The present invention will be described in detail below to facilitate its implementation by those skilled in the art. However, the present invention can be implemented in various different forms and is not limited to the embodiments described herein. Furthermore, the scope of protection defined by the patent claims is not intended to be limited.

[0047] In addition, unless otherwise defined, technical and scientific terms used in the description of the present invention have meanings commonly understood by a person of ordinary skill in the art to which this invention pertains, and descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted in the following description.

[0048] The numerical ranges used herein include lower and upper limits and all values ​​within those ranges, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specified in the specification of the present invention, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0049] Unless otherwise specified herein, the statement that a part "includes" a component does not exclude other components, but rather implies the inclusion of other components, unless otherwise specifically stated. Furthermore, the singular forms "a," "an," and "the" as used in the specification and the appended claims are intended to include the plural forms, unless the context clearly dictates otherwise.

[0050] The term "CA-CB" in this specification means "having carbon atoms of A or more and B or less", and the term "A to B" means "having carbon atoms of A or more and B or less".

[0051] The term “alkyl” as used herein refers to a monovalent substituent, including both linear and branched forms. The alkyl may have 1 to 7 carbon atoms, specifically 1 to 5 carbon atoms.

[0052] The above alkyl includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, and the like, for example.

[0053] The term “alkoxy” as used herein refers to an -O-alkyl radical, where “alkyl” is as defined above. Specific examples include, but are not limited to, methoxy, ethoxy, i-propoxy, butoxy, i-butoxy, t-butoxy, and the like.

[0054] The term “halogen” as used herein means a group 17 element and may be any one selected from among F, Cl, Br, and I.

[0055] In this specification, “room temperature” may mean a temperature without artificial temperature control, and for example, the room temperature may be 20°C to 40°C, or 20°C to 30°C.

[0056] The term “about” in this specification is used in a sense that is at or near the numerical value when manufacturing and material tolerances inherent in the meaning stated are given, and is used to prevent unscrupulous infringers from unfairly exploiting disclosures that state precise or absolute values ​​to aid in the understanding of this specification and the appended claims.

[0057] Hereinafter, the present invention will be described in detail.

[0058] An antimony-containing thin film deposition composition according to one aspect of the present invention can provide a high-quality antimony-containing thin film by including a precursor compound having a specific structure.

[0059] Specifically, the precursor compound according to one aspect may be an antimony compound represented by the following chemical formula 1.

[0060] [Chemical Formula 1]

[0061]

[0062] In the above chemical formula 1,

[0063] R 1 is C1-C7 alkyl; R 2 is C1-C7 alkyl or C1-C7 alkoxy; A is halogen or C1-C7 alkoxy.

[0064] Although not intended to be bound by a specific theory, the antimony compound represented by the above chemical formula 1 exists in a liquid state at room temperature and may have excellent reactivity and volatility. Accordingly, the composition for depositing an antimony-containing thin film according to one embodiment may be easy to store and handle, and may deposit a thin film at a high thin film deposition rate even under low temperature conditions, and may provide an antimony-containing thin film having high purity and excellent durability.

[0065] In addition, the antimony-containing thin film prepared from the composition for depositing an antimony-containing thin film according to one embodiment is very advantageous in forming a pattern with a smaller feature size than the currently used chemically amplified photoresist (CAR). Although the CAR (Chemically amplified resist) has high sensitivity, its typical elemental makeup of O, F, S, and C makes the photoresist too transparent at a certain wavelength, which has the disadvantage of reducing the sensitivity.

[0066] In addition, CAR (Chemically amplified resist) may have difficulties in pattern formation due to roughness issues in small feature sizes, and has a disadvantage of increasing LER (Line edge roughness) as the photospeed decreases, partly due to the nature of acid-catalyzed processes. On the other hand, the antimony compound according to one embodiment of the present invention has excellent light absorption rate and light emission effect for EUV, and thus can be very usefully used as a hard mask used in the EUV photolithography process.

[0067] Specifically, R in chemical formula 1 according to one embodiment of the present invention 1 is C1-C7 alkyl;

[0068] R2 is C1-C7 alkyl or C1-C7 alkoxy; A may be halogen or C1-C7 alkoxy. For example, the C1-C7 alkyl may be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. Preferably, it may be branched-chain alkyl, and more preferably, it may be i-propyl, i-butyl or t-butyl. In addition, the C1-C7 alkoxy may be methoxy, ethoxy, propoxy or butoxy, and preferably, it may be C1-C3 alkoxy, and specifically, it may be methoxy or ethoxy. The halogen may be any one selected from F, Cl, Br and I, and preferably, it may be I.

[0069] In addition, in the chemical formula 1 according to one embodiment of the present invention, R 1 is C1-C5 alkyl; R 2 is C1-C5 alkyl or C1-C5 alkoxy; A may be halogen or C1-C5 alkoxy.

[0070] The antimony compound represented by the above chemical formula 1 may be represented by, for example, the following chemical formula 2 or 3.

[0071] [Chemical Formula 2]

[0072]

[0073] [Chemical Formula 3]

[0074]

[0075] In the above chemical formulas 2 and 3, R 1 is C1-C5 alkyl; R 3 and R 4 are independently C1-C5 alkyl or C1-C5 alkoxy; R 5 is C1-C5 alkyl; X may be halogen.

[0076] Specifically, in the above chemical formulae 2 and 3, the C1-C5 alkyl may be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. Preferably, it may be branched-chain alkyl, and more preferably, it may be i-propyl, i-butyl or t-butyl. In addition, the C1-C7 alkoxy may be methoxy, ethoxy, propoxy or butoxy, and preferably, it may be C1-C3 alkoxy, and specifically, it may be methoxy or ethoxy. The halogen may be any one selected from F, Cl, Br and I, and preferably, it may be I.

[0077] The antimony compound represented by the above chemical formula 1 may be selected from, for example, the following compounds, but is not limited thereto.

[0078]

[0079]

[0080]

[0081] (In the above structure, Me means methyl, Et means ethyl, and Pr means n-propyl or i-propyl.)

[0082] According to one aspect, an antimony-containing thin film deposition composition necessarily includes an antimony compound represented by the above chemical formula 1 as a precursor for thin film deposition, and the content of the compound represented by the above chemical formula 1 in the composition may be included within a range that can be recognized by a person skilled in the art in consideration of 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. In addition, another aspect of the present invention provides a method for producing an antimony-containing thin film using the above antimony-containing thin film deposition composition.

[0083] A method for manufacturing an antimony-containing thin film according to one embodiment can manufacture a high-quality antimony-containing thin film with a high deposition rate even at low temperature and low power by using a composition containing an antimony compound represented by the above chemical formula 1 as a precursor. The antimony-containing thin film can be used for various purposes, for example, as an insulating film, a diffusion barrier film, a hard mask, an etch stop layer, a seed layer, a spacer, an antireflection layer, an intermetallic dielectric material, and a protective film layer in the manufacture of electronic devices, and can preferably be used as a hard mask used in an EUV photolithography process, but is not limited thereto.

[0084] In the 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 commonly used in the relevant field, but 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, and specifically, ALD, CVD, or PEALD can be used, but is not limited thereto.

[0085] A method for manufacturing an antimony-containing thin film according to one aspect is as follows:

[0086] a) A step of maintaining the temperature of a substrate mounted in a chamber at 30 to 500°C;

[0087] b) It may include a step of forming an antimony-containing thin film by injecting a composition for depositing an antimony-containing thin film according to one aspect of the present invention and a reaction gas onto a substrate.

[0088] The method for manufacturing the antimony-containing thin film according to one embodiment may further include a step of purging the composition for residual deposition, reaction gas, and byproducts.

[0089] The substrate is not particularly limited as long as it is commonly used in the relevant field, but may be, for example, a substrate including one or more semiconductor materials of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a silicon on insulator (SOI) substrate; a quartz substrate; or a glass substrate for a display; a flexible plastic substrate such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), or polyester.

[0090] In addition, in addition to forming a thin film directly on the substrate, the antimony-containing thin film may further form a plurality of conductive layers, dielectric layers, or insulating layers between the substrate and the antimony-containing thin film.

[0091] For example, the temperature of the substrate may be controlled to, but is not limited to, 30 to 500°C, or 30 to 300°C, or 50 to 300°C.

[0092] For example, the reaction gas may be supplied after being activated by generating plasma of 20 to 1,000 W, or 20 to 800 W, or 50 to 600 W.

[0093] Specifically, the method for manufacturing an antimony-containing thin film according to one aspect can effectively manufacture a thin film even at low temperature and low plasma generation by using the compound of the above chemical formula 1 as a precursor.

[0094] The above reaction gas can remove the ligand of the antimony compound included in the antimony-containing thin film deposition composition to form an antimony-containing atomic layer.

[0095] The type of the above reaction gas is not particularly limited as long as it is commonly used in the relevant field, but may be, for example, oxygen (O2), ozone (O3), oxygen plasma, hydrogen (H2), hydrogen plasma, water (H2O), hydrogen peroxide (H2O2), nitrogen (NO2), nitrogen monoxide (NO), nitrous oxide (N2O), ammonia (NH3), carbon dioxide (CO2), formic acid (HCOOH), acetic acid (CH3COOH), acetic anhydride ((CH3CO)2O), or a combination thereof.

[0096] For example, the concentration of ozone in the reaction gas is 10 to 220 g / m 3 It may be, but is not limited to,

[0097] In a method for manufacturing an antimony-containing thin film according to one embodiment, an inert gas may be used as a transport gas or purge gas. The type of the transport gas or purge gas is not particularly limited as long as it is one commonly used in the relevant field. For example, argon, nitrogen, krypton, etc. may be used, and argon is preferred due to its economical nature.

[0098] In one embodiment, the method for manufacturing an antimony-containing thin film can adjust the deposition conditions according to the structure or thermal characteristics of the desired thin film, and examples of the deposition conditions according to one embodiment include the input flow rate of the antimony-containing thin film deposition composition including the compound of the above chemical formula 1, the input flow rate of the reaction gas and the transport gas, the pressure, the RF power, the substrate temperature, etc. As a non-limiting example, the input flow rate of the antimony-containing thin film deposition composition is 10 to 1000 cc / min, the transport 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.

[0099] In addition, another aspect of the present invention provides a novel compound usable as a precursor for an antimony-containing thin film. Specifically, the novel compound may be an antimony compound represented by the following chemical formula 1.

[0100] [Chemical Formula 1]

[0101]

[0102] In the above chemical formula 1, R 1 is C1-C7 alkyl; R 2 is C1-C7 alkyl or C1-C7 alkoxy; A may be halogen or C1-C7 alkoxy. Specifically, in the above chemical formula 1, the C1-C7 alkyl may be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or n-pentyl, i-pentyl, neo-pentyl. Preferably, it may be branched-chain C3-C5 alkyl, and more preferably, it may be t-butyl. In addition, the C1-C7 alkoxy may be methoxy, ethoxy, propoxy, or butoxy, and preferably, it may be ethoxy. The halogen may be any one selected from F, Cl, Br, and I, and preferably, it may be I. However, the R 1 This is t-butyl and R 2and A are both ethoxy.

[0103] The antimony compound represented by the above chemical formula 1 may be represented by, for example, the following chemical formula 2 or 3.

[0104] [Chemical Formula 2]

[0105]

[0106] [Chemical Formula 3]

[0107]

[0108] In the above chemical formulas 2 and 3, R 1 is C1-C5 alkyl; and R 3 and R 4 are independently C1-C5 alkyl or C1-C5 alkoxy; R 5 is C1-C5 alkyl; X may be I.

[0109] However, the above R 1 This is t-butyl and R 4 This is ethoxy and R 5 Except for this ethyl case.

[0110] The antimony compound according to one embodiment of the present invention can be produced by any method possible by a person skilled in the art.

[0111] Hereinafter, the above-described implementation examples will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the rights.

[0112] The physical properties of the examples below were measured as follows.

[0113] 1) Elemental composition analysis

[0114] The elemental composition of the thin film was analyzed using an X-ray photoelectron spectrometer (K-Alpha+, 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(t-butyl)iodoantimony

[0118]

[0119] 120 g (0.53 mol) of antimony trichloride (SbCl3) was added to a 10 L flask, followed by 3,000 ml of ether, and the mixture was stirred while maintaining an internal temperature of 10°C. 526 ml (1.06 mol) of t-butylmagnesium chloride (2.0 M solution in ether) was slowly added to the flask while maintaining an internal temperature of 10°C, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the residue was removed through a filter, and the solvent and byproducts were removed under reduced pressure. Thereafter, the mixture was purified at 42°C and 0.4 Torr, thereby synthesizing 70 g of bis(t-butyl)antimonychloride.

[0120] 1 H NMR (C6D6): δ 1.18(s, 18H)

[0121] 16.7 g (0.11 mol) of NaI was added to a 1 L flask, followed by 300 ml of hexane, and the mixture was stirred while maintaining the internal temperature at 20°C. 30 g (0.11 mol) of prepared bis(t-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(t-butyl)iodoantimony. After completion of the reaction, the residue was removed through a filter, and the solvent and byproducts were removed under reduced pressure to obtain bis(t-butyl)iodoantimony. Thereafter, the product was purified at 44°C and 0.24 Torr to obtain 30 g of bis(t-butyl)iodoantimony.

[0122] 1 H NMR (C6D6): δ 1.28(s, 18H)

[0123] Figure 1 shows the TGA analysis results of the bis(t-butyl)iodoantimony prepared in Example 1, from which it can be seen that the antimony compound of Example 1 has a single evaporation step starting from about 140°C, and the residue mass at 500°C is confirmed to be 23.0%, indicating rapid evaporation characteristics. These results show that the antimony compound of Example 1 has excellent thermal stability.

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

[0125]

[0126] In a 500 ml flask, 5.52 g (0.08 mol) of NaOEt was added, followed by 100 ml of ethanol, and the mixture was stirred while maintaining the internal temperature at 20°C. 22 g (0.08 mol) of prepared bis(t-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(t-butyl)ethoxyantimony. After completion of the reaction, the residue was removed through a filter, and the solvent and byproducts were removed under reduced pressure to obtain bis(t-butyl)ethoxyantimony (13 g). Thereafter, the product was purified at 22°C and 0.41 Torr to obtain 8 g of bis(t-butyl)ethoxyantimony.

[0127] 1 H NMR (C6D6): δ 3.96(q, 2H), 1.24(s, 18H), 1.20(t, 3H)

[0128] Figure 2 shows the TGA analysis results of the bis(t-butyl)ethoxyantimony prepared in Example 2, from which it can be seen that the antimony compound of Example 2 has a single evaporation step starting from about 70°C, and the residue mass at 500°C is confirmed to be 2.9%, indicating rapid evaporation characteristics. These results show that the antimony compound of Example 2 has excellent thermal stability.

[0129] [Example 3] Preparation of t-butylbisethoxyantimony

[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. While maintaining the internal temperature of the mixture at -10°C, 19 g (0.41 mol) of dimethylamine was slowly added, and the mixture was stirred at room temperature (25°C) for 2 hours to synthesize lithium (dimethylamine) (Li(Dimethylamine)).

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

[0133] 65 ml (0.13 mol) of t-butylmagnesium chloride (2.0 M solution in ether) was slowly added to the flask while maintaining the internal temperature at -20°C and stirred at room temperature for 4 hours. After completion of the reaction, the solvent and byproducts were removed under reduced pressure. Thereafter, 15 g of t-butylbis(dimethylamino)antimony was synthesized by purification at 30°C and 0.4 Torr.

[0134] 1 H-NMR (C6D6): δ 2.78 (s, 12H), 1.19 (s, 9H)

[0135] 15.0 g (0.06 mol) of t-butylbis(dimethylamino)antimony was added to a 500 mL flask, followed by 60 mL of hexane and stirring 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 t-butylbisethoxyantimony. After completion of the reaction, the residue was removed through a filter, and the solvent and byproducts were removed under reduced pressure to obtain 12 g of t-butylbisethoxyantimony.

[0136] Afterwards, purification was performed at 16 ℃ and 0.49 Torr pressure to obtain 10 g of t-butylbisethoxyantimony.

[0137] 1 H-NMR (C6D6): δ 4.01 (q, 4H), 1.21 (s, 9H), 1.20 (t, 6H)

[0138] Figure 3 shows the TGA analysis results of t-butylbisethoxyantimony prepared in Example 3, from which it can be seen that the antimony compound of Example 3 has a single evaporation step starting from about 100°C, and the residue mass at 500°C is confirmed to be 5.0%, indicating rapid evaporation characteristics. These results show that the thermal stability of the antimony compound of Example 3 is very excellent.

[0139] [Example 4]

[0140] Antimony oxide thin films were prepared by plasma enhanced atomic layer deposition using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony and t-butylbisethoxyantimony prepared in Examples 1 to 3 as antimony precursors.

[0141] The substrate on which the antimony oxide thin film was to be formed was a silicon substrate, and the silicon substrate was transferred into a deposition chamber and maintained at a constant temperature.

[0142] The temperature of the stainless steel canister filled with the antimony precursor was maintained to ensure a constant vapor pressure of the precursor. The vaporized antimony precursor was transported into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. Subsequently, a purge process was performed using argon gas. Oxygen gas was used as the reaction gas, and the reaction process was performed using a constant plasma power. In addition, a purge process was performed using argon gas to remove reaction byproducts. The above-mentioned atomic layer deposition process was repeated for a certain number of cycles, one cycle, to form an antimony oxide thin film. The detailed deposition conditions are shown in Table 1 below.

[0143] As shown in Table 1, the composition of the antimony oxide thin film deposited for each precursor under certain conditions was analyzed using X-ray photoelectron spectroscopy. Carbon and iodine were not detected, confirming that a pure antimony oxide thin film could be obtained.

[0144] Precursor substrate temperature Precursor vapor pressure Precursor injection Purge reaction Purge cycle Argon bubble time Argon time Oxygen plasma power time Argon time [℃] [Torr] [sccm] [sec] [sccm] [sec] [sccm] [W] [sec] [sccm] [sec] [No.] Example 1 2000.550 1600 5600 500 2600 5500 Example 2 2000.550 1600 5600 500 2600 5500 Example 3 2000.550 1600 5600 500 2600 5500

[0145] [Example 5]

[0146] An antimony oxide thin film was prepared by atomic layer deposition using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony and t-butylbisethoxyantimony prepared in Examples 1 to 3 as antimony precursors.

[0147] The substrate on which the antimony oxide thin film was to be formed was a silicon substrate, and the silicon substrate was transferred into a deposition chamber and maintained at a constant temperature.

[0148] The temperature of the stainless steel canister filled with the antimony precursor was maintained to ensure a constant vapor pressure of the precursor. The vaporized antimony precursor was transported into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. Subsequently, a purge process was performed using argon gas. The reaction process was performed using a certain concentration of ozone gas as a reaction gas. In addition, a purge process was performed using argon gas to remove reaction byproducts. The above atomic layer deposition process was repeated for a certain number of cycles, one cycle, to form an antimony oxide thin film. The detailed deposition conditions are shown in Table 2 below.

[0149] As shown in Table 2, the composition of the antimony oxide thin film deposited for each precursor under certain conditions was analyzed using X-ray photoelectron spectroscopy. Carbon and iodine were not detected, confirming that a pure antimony oxide thin film could be obtained.

[0150] Precursor substrate temperature Precursor vapor pressure Precursor injection Purge reaction Purge cycle Argon bubble time Argon time Ozone Ozone concentration time Argon time [℃] [Torr] [sccm] [sec] [sccm] [sec] [sccm] [g / m³] [sec] [sccm] [sec] [No.] Example 1 2000.550 1600 5600 220 5600 20 500 Example 2 2000.550 1600 5600 220 5600 20 500 Example 3 2000.550 1600 5600 220 5600 20 500

[0151] [Example 6]

[0152] Antimony-containing thin films were prepared by plasma enhanced atomic layer deposition using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony and t-butylbisethoxyantimony prepared in Examples 1 to 3 as antimony precursors.

[0153] 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.

[0154] The temperature of the stainless steel canister filled with the antimony precursor was maintained to ensure a constant vapor pressure of the precursor. The vaporized antimony precursor was transported into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. Subsequently, a purge process was performed using argon gas. Carbon dioxide gas was used as the reaction gas, and the reaction process was performed using a constant plasma power. In addition, a purge process was performed using argon gas to remove reaction byproducts. The above-mentioned atomic layer deposition process was repeated for a certain number of cycles, defining one cycle, to form an antimony-containing thin film. The detailed deposition conditions are shown in Table 3 below.

[0155] As shown in Table 3, the composition of the antimony oxide thin film deposited for each precursor under certain conditions was analyzed through X-ray photoelectron spectroscopy, and the results are shown in Table 4 below. It was confirmed that the thin film formed with bis(t-butyl)iodoantimony contained carbon and iodine in addition to antimony, and it was confirmed that the thin film formed with bis(t-butyl)ethoxyantimony or t-butylbisethoxyantimony contained carbon in addition to antimony.

[0156] Precursor substrate temperature Precursor vapor pressure Precursor injection Purge reaction Purge cycle Argon bubble time Argon time Carbon dioxide plasma power time Argon time [℃] [Torr] [sccm] [sec] [sccm] [sec] [sccm] [W] [sec] [sccm] [sec] [No.] Example 1 700.550 1600 5600 50 2600 5500 Example 2 700.550 1600 5600 50 2600 5500 Example 3 700.550 1600 5600 50 2600 5500

[0157] X-ray photoelectron analysis results Precursor SbIOC at% at% at% at% Example 1 40.03.0 39.8 17.2 Example 2 41.2 0 41.1 17.7 Example 3 41.8 0 40.0 18.2

[0158] [Example 7]

[0159] An antimony-containing thin film was prepared by chemical vapor deposition using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony and t-butylbisethoxyantimony prepared in Examples 1 to 3 as antimony precursors.

[0160] The substrate on which the antimony-containing thin film was to be formed was a silicon substrate, and the silicon substrate was transferred into a deposition chamber and maintained at a constant temperature.

[0161] The temperature of the stainless steel bubbler-type canister filled with the antimony precursor was maintained so that the vapor pressure of the precursor was constant. The vaporized antimony precursor was transported into the chamber using argon gas as a transport gas. In addition, water vapor was used as the reaction gas, and the water vapor was transported into the chamber using argon gas as a transport gas while maintaining the temperature of the stainless steel canister filled with water so that the vapor pressure was constant. In addition, the process pressure was controlled using a throttle valve so that the pressure in the chamber was constant. In this way, a chemical vapor deposition method 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.

[0162] As shown in Table 5, the composition of antimony oxide thin films deposited for each precursor under certain conditions was analyzed using X-ray photoelectron spectroscopy. It was confirmed that the thin films formed with bis(t-butyl)iodoantimony contained carbon and iodine in addition to antimony, and it was confirmed that the thin films formed with bis(t-butyl)ethoxyantimony or t-butylbisethoxyantimony contained carbon in addition to antimony.

[0163] Precursor Substrate Temperature Precursor Water Transport Gas Argon Process Pressure Deposition Time Vapor Pressure Argon Bubble Vapor Pressure Argon Bubble [℃] [Torr] [sccm] [Torr] [sccm] [sccm] [Torr] [sec] Example 1 700.2256 10600 3600 Example 2 700.2256 10600 3600 Example 3 700.2256 10600 3600

[0164] [Example 8] Patterning of an antimony-containing thin film

[0165] An antimony-containing thin film was formed as in Example 6 using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony and t-butylbisethoxyantimony prepared in Examples 1 to 3 as antimony precursors.

[0166] 70 to 80 mJ / cm in EUV lithography equipment to form 1:1 line-space features at a pitch of 24 nm. 2 The film was patterned using EUV with exposure to . Subsequently, it was baked at 150°C for 3 minutes, developed in 2-heptanone for 15 seconds, and rinsed with the same solvent.

[0167] The results of scanning electron microscope analysis of line / space patterns formed on a silicon substrate with pitches of 24 nm are shown in Fig. 4, and it was confirmed that a 1:1 line / space pattern was evenly formed even with a narrow pitch of 24 nm.

Claims

1. A composition for depositing an antimony-containing thin film, comprising an antimony compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R 1 is C1-C7 alkyl; R 2 is C1-C7 alkyl or C1-C7 alkoxy; A is halogen or C1-C7 alkoxy.

2. In paragraph 1, The above R 1 is C1-C5 alkyl; R 2 is C1-C5 alkyl or C1-C5 alkoxy; A composition for thin film deposition containing antimony, which is a halogen or C1-C5 alkoxy.

3. In paragraph 1, An antimony compound represented by the above chemical formula 1 is an antimony-containing thin film deposition composition represented by the following chemical formula 2 or 3: [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 2 and 3, R 1 is C1-C5 alkyl; R 3 and R 4 are independently C1-C5 alkyl or C1-C5 alkoxy; R 5 is C1-C5 alkyl; X is a halogen.

4. In paragraph 1, A composition for depositing an antimony-containing thin film, wherein the antimony compound is selected from the following compounds. (In the above structure, Me is methyl, Et is ethyl, and Pr is n-propyl or i-propyl.) 5. A method for producing an antimony-containing thin film using an antimony-containing thin film deposition composition according to any one of claims 1 to 4.

6. In paragraph 5, The above manufacturing method a) A step of maintaining the temperature of a substrate mounted in a chamber at 30 to 500°C; b) A method for manufacturing an antimony-containing thin film, comprising the step of forming an antimony-containing thin film by injecting a composition for depositing an antimony-containing thin film according to any one of claims 1 to 4 and a reaction gas onto a substrate.

7. In paragraph 6, A method for producing an antimony-containing thin film, wherein the reaction gas comprises oxygen (O2), ozone (O3), oxygen plasma, hydrogen (H2), hydrogen plasma, water (H2O), hydrogen peroxide (H2O2), nitrogen (NO2), nitrogen monoxide (NO), nitrous oxide (N2O), ammonia (NH3), carbon dioxide (CO2), formic acid (HCOOH), acetic acid (CH3COOH), acetic anhydride ((CH3CO)2O), or a combination thereof.

8. In paragraph 6, A method for manufacturing an antimony-containing thin film, wherein the above reaction gas is supplied after being activated by generating plasma of 20 to 1,000 W.

9. An antimony compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R 1 is C1-C7 alkyl; R 2 is C1-C7 alkyl or C1-C7 alkoxy; A is halogen or C1-C7 alkoxy; However, the above R 1 This is t-butyl and R 2 and A are both ethoxy.

10. In paragraph 9, The above antimony compound is an antimony compound represented by the following chemical formula 2 or 3: [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 2 and 3, R 1 is C1-C5 alkyl; R 3 and R 4 are independently C1-C5 alkyl or C1-C5 alkoxy; R 5 is C1-C5 alkyl; X is I; However, the above R 1 This is t-butyl and R 4 This is ethoxy and R 5 Except for this ethyl case.

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