Antimony-containing thin film deposition composition and method for producing an antimony-containing thin film using the same

Abstract

The present invention relates to an antimony-containing thin film deposition composition containing an antimony compound that can be usefully used as a precursor for antimony-containing thin films, and to a method for producing an antimony-containing thin film using the same. The antimony compound according to the embodiment exists in a liquid state at room temperature, is easy to store and handle, and has high reactivity, so it can be used to efficiently form a metal thin film.

Description

[Technical Field]

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

[0002] Antimony (Sb)-containing thin films exhibit excellent thin-film properties and can be used as insulating films, diffusion-blocking films, hard masks, etching stop layers, seed layers, spacers, intermetallic dielectric materials, protective film layers, and anti-reflective layers, and their application fields are becoming increasingly diverse. In particular, antimony-containing thin films have outstanding etching resistance and are attracting attention as a next-generation material for hard masks in EUV photolithography processes.

[0003] On the other hand, with the increasing performance of devices, semiconductor circuits are becoming smaller every year. Due to the miniaturization of semiconductor circuits, the increase in aspect ratio, and the diversification of device materials, there is a need for technology that can form ultrafine thin films that are uniform and thin even at low temperatures, and that have excellent electrical properties and etching resistance. However, existing antimony-containing thin film precursors involve high-temperature processes, making them difficult to apply to plastic substrates. If the process temperature is lowered, the thin film deposition rate and purity of the thin film may decrease, resulting in limitations in step coverage, etching resistance, and physical and electrical properties. [Overview of the project] [Problems that the invention aims to solve]

[0004] One aspect of the present invention provides an antimony-containing thin film deposition composition that can provide an antimony-containing thin film of excellent quality.

[0005] Furthermore, one aspect of the present invention provides a method for producing an antimony-containing thin film that enables the deposition of a thin film with a high thin-film deposition rate even under mild reaction conditions, and allows for the production of a high-quality antimony-containing thin film with high purity.

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

Means for Solving the Problems

[0007] The present invention provides a composition for depositing an antimony-containing thin film capable of producing an antimony-containing thin film of excellent quality. The composition for depositing an antimony-containing thin film according to one aspect of the present invention can contain an antimony compound represented by the following Chemical Formula 1. [Chemical Formula 1] JPEG2026522425000002.jpg21170 In Chemical Formula 1 above, R 1 is C1-C7 alkyl, R 2 is C1-C7 alkyl or C1-C7 alkoxy, and A is halogen or C1-C7 alkoxy.

[0008] Preferably, in Chemical Formula 1, R 1 is C1-C5 alkyl, R 2 is C1-C5 alkyl or C1-C5 alkoxy, and A may be halogen or C1-C5 alkoxy.

[0009] Preferably, the antimony compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 2 or 3. [Chemical Formula 2] JPEG2026522425000003.jpg21170 [Chemical Formula 3] JPEG2026522425000004.jpg21170

[0010] In Chemical Formulas 2 and 3 above, R 1 is C1-C5 alkyl, R 3 and R 4 are each independently C1-C5 alkyl or C1-C5 alkoxy, R 5 is C1-C5 alkyl, and X is halogen.

[0011] The antimony compound according to one embodiment may be selected from, but is not limited to, the following compounds. JPEG2026522425000005.jpg166170 JPEG2026522425000006.jpg87170(In the above structure, Me means methyl, Et means ethyl, and Pr means n-propyl or i-propyl.)

[0012] Furthermore, the present invention provides a method for manufacturing an antimony-containing thin film using the above-described composition for depositing an antimony-containing thin film.

[0013] The method for manufacturing an antimony-containing thin film according to one embodiment of the present invention a) maintaining the temperature of the substrate mounted in the chamber at 30 to 500 °C; b) injecting the composition for depositing an antimony-containing thin film according to one embodiment of the present invention and a reaction gas onto the substrate to form an antimony-containing thin film.

[0014] The 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.

[0015] The reaction gas may be supplied after generating and activating a plasma of 20 to 1,000 W.

[0016] Moreover, one embodiment of the present invention provides a novel compound that can be used as a precursor for an antimony-containing thin film of excellent quality, and the compound may be an antimony compound represented by the following Chemical Formula 1. [Chemical Formula 1] JPEG2026522425000007.jpg21170

[0017] In 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 when R 1 is t-butyl and both R 2 and A are ethoxy, it is excluded.

[0018] More preferably, according to one aspect, the antimony compound may be represented by the following Chemical Formula 2 or 3. [Chemical Formula 2] JPEG2026522425000008.jpg21170[Chemical Formula 3] JPEG2026522425000009.jpg21170

[0019] In Chemical Formulas 2 and 3, R 1 is C1-C5 alkyl, R 3 and R 4 are independently of each other C1-C5 alkyl or C1-C5 alkoxy, R 5 is C1-C5 alkyl, X is I, provided that when R 1 is t-butyl, R 4 is ethoxy, and R 5 is ethyl, it is excluded. [Advantages of the Invention] [[ID=...]] (omitted for brevity as the original text has some consecutive blank lines which seem to be formatting issues, but following the rules, we keep the line breaks as is) The composition for thin film deposition containing antimony according to one aspect of the present invention can be easily stored and handled, and even under low temperature conditions, thin films can be deposited at a high thin film deposition rate, and an antimony-containing thin film of excellent quality can be produced with high purity.

[0021] Also, the composition for thin film deposition containing antimony according to one aspect of the present invention can produce thin films of excellent quality with a high yield and can be usefully applied to various industrial fields.

[0022] ​​In particular, the antimony compound of the present invention exhibits excellent light absorption and light emission effects for EUV, making it extremely useful as a hard mask used in EUV photolithography processes. [Brief explanation of the drawing]

[0023] [Figure 1] This is the spectrum of the TGA analysis results for bis(t-butyl)iodoantimony produced in Example 1. [Figure 2] This is the spectrum of the TGA analysis results for bis(t-butyl)ethoxyantimony produced in Example 2. [Figure 3] This is the spectrum of the TGA analysis results for (t-butyl)bisethoxyantimony produced in Example 3. [Figure 4] This shows the results of scanning electron microscopy (SEM) analysis of the line / spatial pattern formed in Example 8. [Modes for carrying out the invention]

[0024] The present invention will be described in detail below so that it can be easily implemented by a person with ordinary skill in the art to which the invention pertains. However, this does not limit the embodiments described herein, as the invention can be realized in various different forms. Nor does it limit the scope of protection as defined by the claims.

[0025] Furthermore, unless otherwise defined, technical and scientific terms used in this description have the meanings that are ordinarily understood by a person with ordinary skill in the art to which this invention belongs, and in the following description, explanations of known functions and configurations that may obscure the gist of this invention will be omitted.

[0026] As used herein, numerical ranges include lower and upper limits and all values ​​within those limits, increments logically derived from the form and width of the defined range, all double-limited values, and all possible combinations of upper and lower limits of numerical ranges limited to different forms. Unless otherwise specifically defined in the specification of this 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.

[0027] Unless otherwise specifically defined in this invention, the statement that a part "includes" a certain component means, unless otherwise specifically stated to the contrary, that it may include other components rather than excluding them. Furthermore, the singular form used in the specification and the appended claims may be intended to include plural forms unless otherwise indicated in the context.

[0028] In this specification, the term "CA-CB" means "a carbon atom with a number of carbon atoms greater than or equal to A and less than or equal to B," and the term "A-B" means "a carbon atom greater than or equal to A and less than or equal to B."

[0029] The term "alkyl" as used herein refers to a monovalent substituted compound, and includes both linear and branched forms. The alkyl may have 1 to 7 carbon atoms, specifically 1 to 5 carbon atoms.

[0030] The alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, and pentyl, as examples.

[0031] As used herein, the term "alkoxy" 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, and t-butoxy.

[0032] In this specification, the term "halogen" means a Group 17 element, which may be any one selected from F, Cl, Br, or I.

[0033] In this specification, the term "room temperature" may mean a temperature in which no artificial temperature control is performed, and for example, the room temperature may be 20°C to 40°C, or 20°C to 30°C.

[0034] The term “approximately” in this specification is used in a sense of being close to or from the numerical value of the manufacturing and material tolerances inherent to the meaning referred to, when such a value is presented, in order to facilitate the understanding of this specification and the appended claims, and to prevent unscrupulous infringers from unfairly using any disclosures that refer to exact or absolute numerical values.

[0035] The present invention will be described in detail below.

[0036] One form of the present invention, an antimony-containing thin film deposition composition, contains a precursor compound with a specific structure and can provide a high-quality antimony-containing thin film.

[0037] Specifically, the precursor compound in one state may be an antimony compound represented by the following chemical formula 1.

[0038] [Chemical formula 1] JPEG2026522425000010.jpg21170

[0039] In the aforementioned chemical formula 1, R 1 It is a C1-C7 alkyl group, and R 2 A is a C1-C7 alkyl or C1-C7 alkoxy, and A is a halogen or a C1-C7 alkoxy.

[0040] Although not bound by any particular theory, the antimony compound represented by chemical formula 1 can exist in a liquid state at room temperature and possess excellent reactivity and volatility. As a result, a uniform antimony-containing thin film deposition composition can be easily stored and handled, enabling thin film deposition with a high deposition rate even under low temperature conditions, and providing an antimony-containing thin film with high purity and excellent durability.

[0041] Furthermore, antimony-containing thin films produced from a uniform antimony-containing thin film deposition composition are highly advantageous for forming smaller pitcher-sized patterns than those produced by currently used chemically amplified photoresists (CARs). While CARs have high sensitivity, their typical elemental makeup—O, F, S, and C—makes the photoresist excessively transparent at certain wavelengths, resulting in a decrease in sensitivity.

[0042] Furthermore, chemically amplified resist (CAR) can be problematic for pattern formation due to its small pitcher size and roughness, and partially due to the nature of the acid-catalyzed process, it has the disadvantage of increasing line edge roughness (LER) as the photospeed decreases. On the other hand, an antimony compound according to one embodiment of the present invention exhibits excellent light absorption and light emission effects for EUV, and can be very usefully used as a hard mask in the EUV photolithography process.

[0043] Specifically, in chemical formula 1 according to one embodiment of the present invention, R 1 It is a C1-C7 alkyl group, R 2A is a C1-C7 alkyl or C1-C7 alkoxy, and A may be a halogen or a 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 a branched alkyl, and more preferably, i-propyl, i-butyl, or t-butyl. The C1-C7 alkoxy may be methoxy, ethoxy, propoxy, or butoxy, preferably a C1-C3 alkoxy, and specifically, methoxy or ethoxy. The halogen may be any one selected from F, Cl, Br, and I, and preferably I.

[0044] Furthermore, in chemical formula 1 according to one embodiment of the present invention, the R 1 It is a C1-C5 alkyl group, and R 2 A is a C1-C5 alkyl or C1-C5 alkoxy, and A may be a halogen or a C1-C5 alkoxy.

[0045] The antimony compound represented by the aforementioned chemical formula 1 can, for example, be represented by the following chemical formulas 2 or 3.

[0046] [Chemical formula 2] JPEG2026522425000011.jpg21170

[0047] [Chemical formula 3] JPEG2026522425000012.jpg21170

[0048] In the above chemical formulas 2 and 3, R 1 It is a C1-C5 alkyl group, and R 3 and R 4 These are independently C1-C5 alkyl or C1-C5 alkoxy, and R 5 X is a C1-C5 alkyl group, and X may be a halogen.

[0049] Specifically, in chemical formulas 2 and 3, the C1-C5 alkyl group may be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, or t-butyl. Preferably, it may be a branched alkyl group, and more preferably, it may be i-propyl, i-butyl, or t-butyl. The C1-C7 alkoxy group may be methoxy, ethoxy, propoxy, or butoxy, and preferably, it may be a C1-C3 alkoxy group, specifically, it may be methoxy or ethoxy. The halogen group may be any one selected from F, Cl, Br, and I, and preferably, it may be I.

[0050] The antimony compound represented by chemical formula 1 may be selected from, for example, the following compounds, but is not limited thereto.

[0051] JPEG2026522425000013.jpg166170 JPEG2026522425000014.jpg87170

[0052] (In the above structure, Me represents methyl, Et represents ethyl, and Pr represents n-propyl or i-propyl.)

[0053] A composition for deposition of an antimony-containing thin film in one form always contains an antimony compound represented by chemical formula 1 as a precursor for deposition of a thin film, and the content of the compound represented by chemical formula 1 in the composition can be within a range that can be recognized by a person skilled in the art, taking into consideration the film deposition conditions or thickness of the thin film, the properties of the thin film, the application of the thin film, etc. Another aspect of the present invention provides a method for producing an antimony-containing thin film using the antimony-containing thin film deposition composition.

[0054] The method for producing an antimony-containing thin film by one mode uses a composition containing the antimony compound represented by chemical formula 1 as a precursor, enabling the production of a high-quality antimony-containing thin film with a high deposition rate even at low temperatures and low power. The antimony-containing thin film can be used in a variety of applications, such as insulating films, diffusion-blocking films, hard masks, etching stop layers, seed layers, spacers, anti-reflective layers, intermetallic dielectric materials, and protective film layers in the fabrication of electronic devices. Preferably, it can be used as a hard mask used in the EUV photolithography process, but is not limited thereto.

[0055] A single method for manufacturing an antimony-containing thin film is not particularly limited as long as it is commonly used in the field. 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 are not limited to these.

[0056] A method for producing an antimony-containing thin film in a uniform manner is: a) A step of maintaining the temperature of the substrate mounted in the chamber at 30 to 500°C, b) The step of injecting an antimony-containing thin film deposition composition according to one aspect of the present invention and a reaction gas into a substrate to form an antimony-containing thin film may be included.

[0057] The method for producing the antimony-containing thin film by one mode may further include a step of purging the residual deposition composition, reaction gas, and by-products.

[0058] The substrate is not particularly limited as long as it is commonly used in the field, but may be, for example, a substrate containing one or more semiconductor materials from among Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, an SOI (Silicon On Insulator) substrate, a quartz substrate, a display glass substrate, or a flexible plastic substrate such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), or polyester.

[0059] Furthermore, in addition to forming the antimony-containing thin film directly on the substrate, a number of conductive layers, dielectric layers, or insulating layers can be further formed between the substrate and the antimony-containing thin film.

[0060] For example, the temperature of the substrate can be adjusted to 30-500°C, 30-300°C, or 50-300°C, but is not limited to these settings.

[0061] For example, the reaction gas may be supplied after being activated by generating a plasma of 20-1,000 W, 20-800 W, or 50-600 W.

[0062] Specifically, the method for producing an antimony-containing thin film using a uniform state allows for the effective production of the thin film even at low temperatures and with low plasma generation, by using the compound of chemical formula 1 as a precursor.

[0063] The reaction gas can remove ligands of antimony compounds contained in the antimony-containing thin film deposition composition, thereby forming an antimony-containing atomic layer.

[0064] The type of reaction gas is not particularly limited as long as it is commonly used in the field, but examples 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.

[0065] As an example, the ozone concentration in the reaction gas is 10-220 g / m³. 3 This is possible, but not limited to it.

[0066] In a method for producing an antimony-containing thin film using a single method, an inert gas can be used as the transfer gas or purge gas. The type of the transfer gas or purge gas is not particularly limited as long as it is commonly used in the field, but as an example, argon, nitrogen, krypton, etc. can be used, and argon is preferred because it is economical.

[0067] In the method for producing an antimony-containing thin film using a single approach, the deposition conditions can be adjusted according to the structure or thermal properties of the target thin film. Examples of deposition conditions using a single approach include the input flow rate of the antimony-containing thin film deposition composition containing the compound of chemical formula 1, the input flow rates of the reaction gas and transfer gas, pressure, RF power, and substrate temperature. As a non-limiting example, the input flow rate of the antimony-containing thin film deposition composition is 10 to 1000 cc / min, the transfer gas is 10 to 1000 cc / min, the reaction gas flow rate is 1 to 1500 cc / min, the pressure is 0.5 to 10 torr, and the RF power and substrate temperature are as described above.

[0068] 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 may be an antimony compound represented by the following chemical formula 1.

[0069] [Chemical formula 1] JPEG2026522425000015.jpg21170

[0070] In the above chemical formula 1, R 1 It is a C1-C7 alkyl group, and R 2 A is a C1-C7 alkyl or C1-C7 alkoxy, and A may be a halogen or a 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 a branched-chain C3-C5 alkyl, and more preferably, it may be t-butyl. The C1-C7 alkoxy may be methoxy, ethoxy, propoxy, or butoxy, and preferably ethoxy. The halogen may be any one selected from F, Cl, Br, and I, and preferably I. However, the R 1 is t-butyl, and R 2 This excludes cases where both A and A are ethoxy.

[0071] The antimony compound represented by the aforementioned chemical formula 1 can be represented, for example, by the following chemical formulas 2 or 3.

[0072] [Chemical formula 2] JPEG2026522425000016.jpg21170

[0073] [Chemical formula 3] JPEG2026522425000017.jpg21170

[0074] In the above chemical formulas 2 and 3, R 1 It is a C1-C5 alkyl group, and R3 and R 4 These are independently C1-C5 alkyl or C1-C5 alkoxy, and R 5 is a C1-C5 alkyl group, and X may be I.

[0075] However, the above R 1 is t-butyl, and R 4 is ethoxy, and R 5 Except when it is ethyl.

[0076] The antimony compound according to one embodiment of the present invention can be any method that is possible for those skilled in the art in the field of the present invention.

[0077] The embodiments described above will be explained in more detail below with reference to the examples. However, the following examples are for illustrative purposes only and do not limit the scope of the rights.

[0078] The physical properties of the following examples were measured as follows.

[0079] 1) Elemental composition analysis The elemental composition of the thin film was analyzed using an X-ray photoelectron spectrometer (K-Alpha+, ThermoFisher Scientific).

[0080] 2) Thermogravimetric analysis Thermogravimetric analysis (TGA, L81-II, LINSEIS) was performed by heating the analyte sample at a rate of 10°C / min to 500°C while injecting nitrogen gas at a pressure of 1.5 bar / min.

[0081] [Example 1] Production of bis(t-butyl)iodoantimony JPEG2026522425000018.jpg21170

[0082] 120 g (0.53 mol) of antimonite trichloride (SbCl3) was placed in a 10 L flask, followed by the addition of 3,000 ml of ether, and the mixture was stirred while maintaining the internal temperature at 10°C. 526 ml (1.06 mol) of t-butylmagnesium chloride (2.0 M solution in ether) was gradually 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 by-products were removed under reduced pressure. The mixture was then purified at 42°C and under a pressure of 0.4 Torr to synthesize 70 g of bis(t-butyl)antimonite chloride.

[0083] 1 H NMR (C6D6): δ 1.18(s, 18H)

[0084] 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 an internal temperature of 20°C. 30 g (0.11 mol) of 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 the reaction was complete, the residue was removed through a filter, and the solvent and by-products were removed under reduced pressure to obtain bis(t-butyl)iodoantimony. Subsequently, the mixture was purified at 44°C and under a pressure of 0.24 Torr to obtain 30 g of bis(t-butyl)iodoantimony.

[0085] 1 H NMR (C6D6): δ 1.28(s, 18H)

[0086] Figure 1 shows the TGA analysis results for bis(t-butyl)iodoantimony produced in Example 1. From this, it can be seen that the antimony compound of Example 1 has a single evaporation step from approximately 140°C, and the residual mass was confirmed to be 23.0% at 500°C, indicating rapid vaporization characteristics. From these results, it can be seen that the antimony compound of Example 1 has excellent thermal stability.

[0087] [Example 2] Production of bis(t-butyl)ethoxyantimony JPEG2026522425000019.jpg23170

[0088] 5.52 g (0.08 mol) of NaOEt was added to a 500 ml flask, followed by 100 ml of ethanol, and the mixture was stirred while maintaining an internal temperature of 20°C. 22 g (0.08 mol) of bis(t-butyl)antimonide (Sb(t-Butyl)2Cl) prepared in the flask was added, and the mixture was stirred at room temperature for 4 hours to synthesize bis(t-butyl)ethoxyantimony. After the reaction was complete, the residue was removed through a filter, and the solvent and by-products were removed under reduced pressure to obtain 13 g of bis(t-butyl)ethoxyantimony. Subsequently, the mixture was purified at 22°C and under a pressure of 0.41 Torr to obtain 8 g of bis(t-butyl)ethoxyantimony.

[0089] 1 H NMR (C6D6): δ 3.96(q, 2H), 1.24(s, 18H), 1.20(t, 3H)

[0090] Figure 2 shows the TGA analysis results for bis(t-butyl)ethoxyantimony produced in Example 2. From this, it can be seen that the antimony compound of Example 2 has a single evaporation step from approximately 70°C, and the residual mass was confirmed to be 2.9% at 500°C, indicating rapid vaporization characteristics. From these results, it can be seen that the antimony compound of Example 2 has excellent thermal stability.

[0091] [Example 3] Preparation of t-butylbisethoxyantimony JPEG2026522425000020.jpg21170

[0092] 169 ml (0.41 mol) of n-butyllithium (2.3 M solution in n-hexane) was added to a 500 ml flask, followed by the addition of 300 ml of n-hexane and stirring. The internal temperature of the mixture was maintained at -10°C, and 19 g (0.41 mol) of dimethylamine was gradually added. The mixture was then stirred at room temperature (25°C) for 2 hours to synthesize lithium (dimethylamine) (Li(Dimethylamine)).

[0093] 30 g (0.13 mol) of antimony trichloride (SbCl3) was placed in a 1 L flask, followed by 300 ml of ether, and the mixture was stirred while maintaining an internal temperature of -10°C. 21 g of prepared lithium (dimethylamine) was gradually added to the flask, and the mixture was stirred at room temperature for 4 hours to synthesize trisdimethylaminoantimony. After synthesis, lithium chloride (LiCl) was removed through a filter, and the solvent was removed under vacuum. Then, 300 ml of hexane was added, and the mixture was stirred while maintaining an internal temperature of -20°C.

[0094] 65 ml (0.13 mol) of t-butylmagnesium chloride (2.0 M solution in Ether) was gradually added to the flask while maintaining an internal temperature of -20°C, and the mixture was stirred at room temperature for 4 hours. After the reaction was complete, the solvent and by-products were removed under reduced pressure. Subsequently, the mixture was purified at 30°C and under a pressure of 0.4 Torr to synthesize 15 g of t-butylbis(dimethylamino)antimony.

[0095] 1 H-NMR(C6D6): δ 2.78(s, 12H), 1.19(s, 9H)

[0096] 15.0 g (0.06 mol) of t-butylbis(dimethylamino)antimony was placed in a 500 mL flask, followed by the addition of 60 mL of hexane, and the mixture was thoroughly stirred. While maintaining the internal temperature of the solution at -40°C, 5.18 g (0.12 mol) of ethanol was gradually added, and the mixture was stirred at room temperature for 4 hours to synthesize t-butylbisethoxyantimony. After the reaction was complete, the residue was removed through a filter, and the solvent and by-products were removed under reduced pressure to obtain 12 g of t-butylbisethoxyantimony.

[0097] Subsequently, the solution was purified at a temperature of 16°C and a pressure of 0.49 Torr to obtain 10 g of t-butylbisethoxyantimony.

[0098] 1 H-NMR(C6D6): δ 4.01(q, 4H), 1.21(s, 9H), 1.20(t, 6H)

[0099] Figure 3 shows the TGA analysis results for t-butylbisethoxyantimony produced in Example 3. From this, it can be seen that the antimony compound of Example 3 has a single evaporation step from approximately 100°C, and the residual mass was confirmed to be 5.0% at 500°C, indicating rapid vaporization characteristics. These results show that the antimony compound of Example 3 has excellent thermal stability.

[0100] [Example 4] Antimony oxide thin films were fabricated using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony, and t-butylbisethoxyantimony, which were prepared in Examples 1-3, as antimony precursors, by plasma-enhanced atomic layer deposition.

[0101] A silicon substrate was used as the substrate on which the antimony oxide thin film was formed. The silicon substrate was transferred into the deposition chamber and a predetermined temperature was maintained.

[0102] A stainless steel canister filled with antimony precursor was kept at a constant temperature to maintain a constant vapor pressure of the precursor. The vaporized antimony precursor was transferred into a chamber using argon gas as the transfer gas and adsorbed onto a silicon substrate. Subsequently, a purging process was performed using argon gas. The reaction process was carried out using oxygen gas as the reaction gas and a predetermined plasma power. Furthermore, a purging process was performed using argon gas to remove reaction byproducts. The above atomic layer deposition process constituted one cycle, and a predetermined cycle was repeated to form an antimony oxide thin film. The detailed deposition conditions are shown in Table 1 below.

[0103] As shown in Table 1, the composition of antimony oxide thin films deposited under predetermined conditions for each precursor was analyzed by X-ray photoelectron spectroscopy. No carbon or iodine was detected, confirming that pure antimony oxide thin films can be obtained.

[0104] [Table 1]

[0105] [Example 5] Antimony oxide thin films were fabricated by atomic layer deposition using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony, and t-butylbisethoxyantimony, which were prepared in Examples 1-3, as antimony precursors.

[0106] A silicon substrate was used as the substrate on which the antimony oxide thin film was formed. The silicon substrate was transferred into the deposition chamber and maintained at a predetermined temperature.

[0107] A stainless steel canister filled with antimony precursor was kept at a constant temperature to maintain a constant vapor pressure of the precursor. The vaporized antimony precursor was transferred into a chamber using argon gas as the transfer gas and adsorbed onto a silicon substrate. Subsequently, a purging process was carried out using argon gas. The reaction process was carried out using ozone gas at a predetermined concentration as the reaction gas. Furthermore, a purging process was carried out using argon gas to remove reaction byproducts. The above atomic layer deposition process constituted one cycle, and a predetermined cycle was repeated to form an antimony oxide thin film. The detailed deposition conditions are shown in Table 2 below.

[0108] As shown in Table 2, the composition of antimony oxide thin films deposited under predetermined conditions for each precursor was analyzed by X-ray photoelectron spectroscopy. Carbon and iodine were not detected, confirming that pure antimony oxide thin films can be obtained.

[0109] [Table 2]

[0110] [Example 6] Antimony-containing thin films were fabricated using plasma-enhanced atomic layer deposition (PLA) with bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony, and t-butylbisethoxyantimony, which were prepared in Examples 1-3, as antimony precursors.

[0111] A silicon substrate was used as the substrate on which the antimony-containing thin film was formed. The silicon substrate was transferred into the deposition chamber and maintained at a predetermined temperature.

[0112] A stainless steel canister filled with antimony precursor was kept at a constant temperature to maintain a constant vapor pressure of the precursor. The vaporized antimony precursor was transferred into a chamber using argon gas as the transport gas and adsorbed onto a silicon substrate. Subsequently, a purging process was performed using argon gas. The reaction process was carried out using carbon dioxide gas as the reaction gas and a predetermined plasma power. Furthermore, a purging process was performed using argon gas to remove reaction byproducts. The above atomic layer deposition process constituted one cycle, and an antimony-containing thin film was formed by repeating a predetermined cycle. The detailed deposition conditions are shown in Table 3 below.

[0113] As shown in Table 3, the composition of antimony oxide thin films deposited under predetermined conditions for each precursor was analyzed by 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.

[0114] [Table 3]

[0115] [Table 4]

[0116] [Example 7] Antimony-containing thin films were prepared by chemical vapor deposition using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony, and t-butylbisethoxyantimony, which were manufactured in Examples 1-3, as antimony precursors.

[0117] A silicon substrate was used as the substrate on which the antimony-containing thin film was formed. The silicon substrate was transferred into a deposition chamber and maintained at a predetermined temperature.

[0118] A stainless steel bubbler-type canister filled with antimony precursor was kept at a constant temperature to maintain a constant vapor pressure of the precursor. The vaporized antimony precursor was transferred into the chamber using argon gas as the transfer gas. Alternatively, water vapor was used as the reaction gas. The water vapor was used to maintain a predetermined vapor pressure in a stainless steel canister filled with water, and the temperature was maintained while argon gas was transferred into the chamber. The process pressure was adjusted using a throttle valve to maintain a constant pressure in the chamber. In this way, an antimony-containing thin film was formed by chemical vapor deposition using antimony precursor and water vapor. The detailed deposition conditions are shown in Table 5 below.

[0119] As shown in Table 5, the composition of antimony oxide thin films deposited under predetermined conditions for each precursor was analyzed by X-ray photoelectron spectroscopy. It was confirmed that the thin film formed with bis(t-butyl)iodoantimony contained carbon and iodine in addition to antimony, and that the thin film formed with bis(t-butyl)ethoxyantimony or t-butylbisethoxyantimony contained carbon in addition to antimony.

[0120] [Table 5]

[0121] [Example 8] Patterning of antimony-containing thin film Using bis(t-butyl)iodoantimony, bis(t-butyl)ethoxyantimony, and t-butylbisethoxyantimony, which were prepared in Examples 1-3, as antimony precursors, antimony-containing thin films were formed as in Example 6.

[0122] Equipped with EUV lithography, 70-80 mJ / cm² is used to form a 1:1 line-space pitcher with a 24nm pitch. 2 Patterning was performed using EUV under the specified exposure. Then, the images were baked at 150°C for 3 minutes, developed with 2-heptanone for 15 seconds, and rinsed with the same solvent.

[0123] Figure 4 shows the results of scanning electron microscopy analysis of line / space patterns formed on a silicon substrate with a pitch of 24 nm. It was confirmed that a uniform 1:1 line / space pattern was formed even with a narrow pitch of 24 nm.

Claims

1. A composition for deposition of antimony-containing thin films, comprising an antimony compound represented by the following chemical formula 1. [Chemical formula 1] In the aforementioned chemical formula 1, R １ It is a C1-C7 alkyl group, R ２ These are C1-C7 alkyl or C1-C7 alkoxy, A is a halogen or a C1-C7 alkoxy.

2. R １ It is a C1-C5 alkyl group, R ２ These are C1-C5 alkyl or C1-C5 alkoxy, The antimony-containing thin film deposition composition according to claim 1, wherein A is a halogen or a C1-C5 alkoxy.

3. The antimony compound represented by chemical formula 1 is represented by the following chemical formula 2 or 3, in the antimony-containing thin film deposition composition according to claim 1. [Chemical formula 2] [Chemical formula 3] In the aforementioned chemical formulas 2 and 3, R １ It is a C1-C5 alkyl group, R ３ and R ４ These are independently C1-C5 alkyl or C1-C5 alkoxy, R ５ It is a C1-C5 alkyl group, X is a halogen.

4. The antimony compound is selected from the following compounds, the antimony-containing thin film deposition composition according to claim 1. (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 the antimony-containing thin film deposition composition described in any one of claims 1 to 4.

6. a) A step of maintaining the temperature of the substrate mounted in the chamber at 30 to 500°C, b) A method for producing an antimony-containing thin film according to claim 5, comprising the step of injecting an antimony-containing thin film deposition composition and a reaction gas according to any one of claims 1 to 4 into the substrate to form an antimony-containing thin film.

7. The reaction gas is oxygen (O ２ ), ozone (O ３ ), oxygen plasma, hydrogen (H ２ ), hydrogen plasma, water (H ２ O), hydrogen peroxide (H ２ O ２ ), nitrogen dioxide (NO ２ ), nitric oxide (NO), nitrous oxide (N ２ O), ammonia (NH ３ ), carbon dioxide (CO ２ ), formic acid (HCOOH), acetic acid (CH ３ COOH), acetic anhydride ((CH ３ CO) ２ O) or a combination thereof, a method for producing the antimony-containing thin film according to claim 6.

8. A method for producing an antimony-containing thin film according to claim 6, wherein the reaction gas is supplied after generating and activating a plasma of 20 to 1,000 W.

9. An antimony compound represented by the following chemical formula 1. [Chemical formula 1] In the aforementioned chemical formula 1, R １ It is a C1-C7 alkyl group, R ２ These are C1-C7 alkyl or C1-C7 alkoxy, A is a halogen or a C1-C7 alkoxy, However, the R １ is t-butyl, and the R ２ This excludes cases where all of A are ethoxy.

10. The antimony compound according to claim 9, represented by the following chemical formula 2 or 3. [Chemical formula 2] [Chemical formula 3] In the aforementioned chemical formulas 2 and 3, R １ It is a C1-C5 alkyl group, R ３ and R ４ These are independently C1-C5 alkyl or C1-C5 alkoxy, R ５ It is a C1-C5 alkyl group, X is I, However, the R １ is t-butyl, and the R ４ is ethoxy, and the R ５ Except when it is ethyl.

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