Iodine-containing metal compound and thin film vapor depositing composition including the same

Abstract

To provide a metal compound containing iodine, a metal-containing thin film vapor depositing composition, and a method for manufacturing a metal-containing thin film using the same.SOLUTION: A thin film vapor depositing composition is present in a liquid state at room temperature, excellent in storage and handling, and has high reactivity, thereby efficiently forming a metal thin film using the same.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a metal compound containing iodine, a composition for metal-containing thin film deposition containing the same, and a method for producing a metal-containing thin film using the composition for thin film deposition. [Background technology]

[0002] Currently used photoresists, chemically amplified resists (CARs), are designed for high sensitivity, but a common elemental composition (mainly C with smaller quantities of O, F, S) can reduce sensitivity by making the photoresist too transparent at a wavelength of 13.5 nm.

[0003] In addition, it has been reported that the process efficiency of CAR decreases due to roughness issues with small pitcher sizes, and that LER (line edge roughness) increases as the photospeed decreases in processes using acid catalysts. To solve this problem, inorganic compounds for EUV (extreme ultraviolet) lithography are required (Korean Patent Publication KR10-2022-0000366A). Summary of the Invention [Problem to be solved by the invention]

[0004] One embodiment provides an iodine-containing metal compound that can be used as a precursor of a metal-containing thin film, and a composition for depositing a metal-containing thin film that includes the same.

[0005] Another embodiment provides a method for preparing a metal-containing thin film using the composition for depositing a metal-containing thin film. [Means for solving the problem]

[0006] One embodiment provides a compound represented by the following formula 1: [Chemical formula 1] [ka] In the above Chemical Formula 1, M is a Group 14, 15 or 16 metal; R 1 is hydrogen or C 1-7 is alkyl, R 2 is C 1-7 is alkyl, R 3 and R 4 are each independently 1-7 Alkyl, C 2-7 Alkenyl or -NR 5 R 6 and R 5 and R 6 are each independently hydrogen or C 1-7 is alkyl, Depending on the metal oxidation number of M, R 3 and R 4 may not be present independently.

[0007] Another embodiment provides a composition for depositing a metal-containing thin film, comprising the iodine-containing metal compound according to the above embodiment.

[0008] Another embodiment provides a method for preparing a metal-containing thin film using the composition for depositing a metal-containing thin film according to the embodiment. Effect of the Invention

[0009] The present disclosure relates to a metal compound containing iodine, a composition for depositing a metal-containing thin film containing the same, and a method for producing a metal-containing thin film using the same. The composition for depositing a thin film according to one embodiment exists in a liquid state at room temperature, has excellent storage and handling properties, and has high reactivity, and therefore can be used to efficiently form a metal thin film. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a diagram showing the results of TGA analysis of t-butylbis(dimethylamino)tin iodide produced in Example 1. [Diagram 2] FIG. 2 shows the results of TGA analysis of tris(dimethylamino)tin iodide produced in Example 2. [Diagram 3] FIG. 2 is a diagram showing the results of TGA analysis of bis(methylamino)antimony iodide produced in Example 3. [Figure 4] FIG. 1 shows the results of TGA analysis of bis(dimethylethylamino)antimony iodide produced in Example 4. [Diagram 5] 1 is a scanning electron microscope image of a line / space pattern formed on a silicon substrate using the tin compound produced in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The embodiments described herein may be modified into various other forms, and the technology according to one embodiment is not limited to the embodiments described below. Furthermore, throughout the specification, "including," "comprising," "containing," or "having" a certain element means that it may further include other elements, and does not exclude elements, materials, or steps not listed, unless otherwise specified to the contrary.

[0012] Numerical ranges used herein include lower and upper limits and all values ​​within the range, increments logically derived by the form and width of the range defined, all values ​​that are doubly limited, and all possible combinations of upper and lower limits of numerical ranges that are limited in different forms. For example, if the content of a composition is limited to 10% to 80% or 20% to 50%, the numerical ranges of 10% to 50% or 50% to 80% should also be interpreted as being described herein. Unless otherwise specified in the present specification, values ​​outside the numerical range that may occur due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0013] Hereinafter, unless otherwise defined in this specification, "about" is understood to mean a value within 30%, 25%, 20%, 15%, 10% or 5% of the specified value.

[0014] As used herein, "alkyl" means a straight or branched chain hydrocarbon composed solely of carbon and hydrogen atoms and can have 1 to 7, 1 to 5, or 1 to 4 carbons.

[0015] As used herein, "alkenyl" refers to a hydrocarbon having one or more carbon-carbon double bonds at any position in the chain, which may be singly or multiply substituted. For example, alkenyl groups may include vinyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, and the like.

[0016] As used herein, a "leaving group" refers to a functional group or atom that can be displaced by a substitution reaction (e.g., a nucleophilic substitution reaction) with another functional group or atom, such as monoC 1-7 Alkylamine or DiC 1-7 It may be, but is not limited to, an alkylamine.

[0017] In this specification, the two alkyl groups contained in a "dialkylamine" may be the same or different.

[0018] One embodiment provides an iodine-containing metal compound represented by the following chemical formula 1:

[0019] [Chemical formula 1] [ka]

[0020] In the above Chemical Formula 1, M is a Group 14, 15 or 16 metal; R 1is hydrogen or C 1-7 is alkyl, R 2 is C 1-7 is alkyl, R 3 and R 4 are each independently 1-7 Alkyl, C 2-7 Alkenyl or -NR 5 R 6 and R 5 and R 6 are each independently hydrogen or C 1-7 is alkyl, Depending on the metal oxidation number of M, R 3 and R 4 may not be present independently.

[0021] According to an embodiment, the iodine-containing metal compound has both a monoalkylamino or dialkylamino group and an iodine group introduced into a metal, and thus when used as a precursor for thin film deposition, it can produce a metal-containing thin film having improved physical properties. In one embodiment, the iodine-containing metal compound contains iodine and a metal, and thus has excellent light absorptivity and / or light emissivity against EUV, and can be effectively used as a hard mask for use in a photolithography process.

[0022] In one embodiment, R 1 and R 2 are each independently a straight or branched chain C 1-7 Alkyl, C 1-5 Alkyl, C 1-4 Alkyl, C 1-3 Alkyl, C 1-2 It can be alkyl or methyl.

[0023] In one embodiment, R 3 and R 4 are each independently a straight or branched chain C 1-7 Alkyl, C 1-6 Alkyl, C 1-5 Alkyl, C1-4 Alkyl, C 1-3 Alkyl, C 1-2 Alkyl, methyl, C 2-7 Alkenyl, C 2-6 Alkenyl, C 2-5 Alkenyl, C 2-4 Alkenyl, C 2-3 In one embodiment, R may be an alkenyl or vinyl (ethenyl). Here, the alkenyl includes those in which the unsaturated carbon is directly connected or the unsaturated carbon is connected via an alkylene. 3 and R 4 are each independently -NR 5 R 6 where R 5 and R 6 are each independently hydrogen or a straight or branched chain C 1-7 Alkyl, C 1-6 Alkyl, C 1-5 Alkyl, C 1-4 Alkyl, C 1-3 Alkyl, C 1-2 It can be alkyl or methyl.

[0024] In one embodiment, M can be Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, or Po, and depending on the metal oxidation number of M, R 3 and / or R 4 may not be present independently.

[0025] In one embodiment, the iodine metal compound may be a compound represented by the following Chemical Formula 2:

[0026] [Chemical formula 2] [ka]

[0027] In the above Chemical Formula 2, M 1 is a Group 14 metal, R 11is hydrogen or C 1-7 is alkyl, R 12 is C 1-7 is alkyl, R 13 and R 14 are each independently 1-7 Alkyl, C 2-7 Alkenyl or -NR 15 R 16 and R 15 and R 16 are each independently hydrogen or C 1-7 It may be alkyl. In one embodiment, the M 1 can be Sn or Te. In one embodiment, R 11 and R 13 are each independently a straight or branched chain C 1-7 Alkyl, C 1-5 Alkyl, C 1-4 Alkyl, C 1-3 Alkyl, C 1-2 It can be alkyl or methyl.

[0028] In one embodiment, R 13 and R 14 are each independently a straight or branched chain C 1-7 Alkyl, C 1-6 Alkyl, C 1-5 Alkyl, C 1-4 Alkyl, C 1-3 Alkyl, C 1-2 Alkyl, methyl, C 2-7 Alkenyl, C 2-6 Alkenyl, C 2-5 Alkenyl, C 2-4 Alkenyl, C 2-3 In one embodiment, R may be an alkenyl or vinyl (ethenyl). Here, the alkenyl includes those in which the unsaturated carbon is directly connected or the unsaturated carbon is connected via an alkylene. 13 and R 14 are each independently -NR 15 R16 where R 15 and R 16 are each independently hydrogen or a straight or branched chain C 1-7 Alkyl, C 1-6 Alkyl, C 1-5 Alkyl, C 1-4 Alkyl, C 1-3 Alkyl, C 1-2 It can be alkyl or methyl.

[0029] In one embodiment, the iodine metal compound may be a compound represented by the following Formula 3:

[0030] [Chemical formula 3] [ka]

[0031] In the above Chemical Formula 3, M 2 is a Group 15 metal, R 21 is hydrogen or C 1-7 is alkyl, R 22 is C 1-7 is alkyl, R 23 is C 1-7 Alkyl, C 2-7 Alkenyl or -NR 25 R 26 and R 25 and R 26 are each independently hydrogen or C 1-7 It may be alkyl.

[0032] In one embodiment, the M 2 can be Sb or Bi.

[0033] In one embodiment, R 21 and R 22 are each independently a straight or branched chain C 1-7 Alkyl, C 1-5Alkyl, C 1-4 Alkyl, C 1-3 Alkyl, C 1-2 It can be alkyl or methyl.

[0034] In one embodiment, R 23 is a linear or branched chain C 1-7 Alkyl, C 1-6 Alkyl, C 1-5 Alkyl, C 1-4 Alkyl, C 1-3 Alkyl, C 1-2 Alkyl, methyl, C 2-7 Alkenyl, C 2-6 Alkenyl, C 2-5 Alkenyl, C 2-4 Alkenyl, C 2-3 In one embodiment, R may be an alkenyl or vinyl (ethenyl). Here, the alkenyl includes those in which the unsaturated carbon is directly connected or the unsaturated carbon is connected via an alkylene. 23 -NR 25 R 26 where R 25 and R 26 are each independently hydrogen or a straight or branched chain C 1-7 Alkyl, C 1-6 Alkyl, C 1-5 Alkyl, C 1-4 Alkyl, C 1-3 Alkyl, C 1-2 It can be alkyl or methyl.

[0035] In one embodiment, the compound represented by formula 2 is [ka] It can be.

[0036] Said M 1 is a Group 14 metal and can be, for example, Sn or Te.

[0037] In one embodiment, the compound represented by formula 3 is [ka] It can be.

[0038] Said M 2 is a Group 15 metal and can be, for example, Sb or Bi.

[0039] However, the specific compounds are merely examples of the compounds represented by Chemical Formula 1, Chemical Formula 2, or Chemical Formula 3, and are not necessarily limited thereto.

[0040] The compounds can be prepared by methods known to those of ordinary skill in the art to which the present disclosure pertains.

[0041] As a specific example, the iodine-containing metal compound represented by Formula 1 according to an embodiment may be prepared by reacting a compound represented by Formula 11 below with a compound represented by Formula 12 below.

[0042] [Chemical formula 11] [ka]

[0043] In the above Chemical Formula 11, M is a Group 14, 15 or 16 metal; R 1 is hydrogen or C 1-7 is alkyl, R 2 is C 1-7 is alkyl, R 3 and R 4 are each independently 1-7 Alkyl, C 2-7 Alkenyl or -NR 5 R 6 and R 5 and R 6are each independently hydrogen or C 1-7 is alkyl, Depending on the metal oxidation number of M, R 3 and R 4 may not exist independently, L is a leaving group.

[0044] [Chemical formula 12] MI x

[0045] In the above Chemical Formula 12, M is a Group 14, 15 or 16 metal; x is selected depending on the oxidation number of M and is an integer of 1 or more.

[0046] M and R in the above Chemical Formula 11 and Chemical Formula 12 1 , R 2 , R 3 , R 4 The above regarding Chemical Formula 1 can be applied.

[0047] According to an embodiment, the method for preparing the iodine-containing metal compound may further include purifying the iodine-containing metal compound represented by Formula 1 at a temperature of about 50° C. to 80° C. or 50° C. to 70° C. and a pressure of 0.1 Torr to 1.0 Torr, or 0.3 Torr to 0.8 Torr after synthesizing the iodine-containing metal compound represented by Formula 1.

[0048] In one embodiment, the organic solvent may be a solvent typically used in organic synthesis, such as hexane, pentane, dichloromethane (DCM), dichloroethane (DCE), toluene, acetonitrile, nitromethane, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and / or N,N-dimethylacetamide (DMA).

[0049] Another embodiment provides a metal-containing thin film deposition composition comprising an iodine-containing metal compound according to an embodiment.

[0050] In one embodiment, the composition for depositing a metal-containing thin film includes an iodine-containing metal compound having a metal-iodine (MI) bond and one or more metal-nitrogen (MN) bonds, thereby improving the reactivity of a metal thin film deposition process using a process such as atomic layer deposition and / or vapor phase deposition, and further increasing the density and purity of the formed metal-containing thin film.

[0051] In addition, the composition for depositing a metal-containing thin film according to an embodiment of the present invention includes an iodine-containing metal compound having a metal and an iodine group, and therefore the metal-containing thin film prepared therefrom has excellent light absorptivity and light emission effect against EUV.

[0052] In one embodiment, the composition for depositing a metal-containing thin film is liquid at room temperature and therefore easy to handle and store. Various thin films with high purity can be produced at a high deposition rate. A thin film produced using the composition for depositing a metal-containing thin film according to one embodiment has excellent durability, electrical properties, and moisture permeability.

[0053] Another embodiment provides a method for preparing a metal-containing thin film using the composition for depositing a metal-containing thin film.

[0054] In one embodiment, the manufacturing method may be applied without limitation as long as it is possible within the scope of what a person of ordinary skill in the art in the technical field disclosed herein can recognize, and may be performed, for example, by atomic layer deposition (ALD), chemical vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), or plasma enhanced atomic deposition (PEALD).

[0055] In one embodiment, the method for producing the metal-containing thin film may include the following steps.

[0056] maintaining the temperature of the substrate mounted in the chamber at 80°C to 400°C; contacting the iodine-containing thin film deposition composition on a substrate so that it is adsorbed on the substrate; and A reaction gas is injected onto the substrate on which the composition for depositing an iodine-containing thin film is adsorbed to form an iodine-containing thin film.

[0057] In one embodiment, the method may further include a step of purging to remove unreacted reactants from around the formed thin film.

[0058] In one embodiment, the reactive gas is oxygen, ozone, distilled water, hydrogen peroxide, nitric oxide, nitrous oxide, nitrogen dioxide, ammonia, nitrogen, hydrazine, amines, diamines, carbon monoxide, carbon dioxide, saturated or unsaturated C 1-12 The gas may be, but is not necessarily limited to, a hydrocarbon, hydrogen, argon and / or helium, or a mixture thereof.

[0059] In the method for producing a metal-containing thin film according to an embodiment, deposition conditions may be adjusted depending on the structure or thermal properties of the target thin film, and examples of the deposition conditions may include the feed flow rate of the composition for depositing a metal-containing thin film according to the embodiment, the feed flow rate of the reaction gas and the carrier gas, pressure, RF power, substrate temperature, etc. For example, the feed flow rate of the composition for depositing a metal-containing thin film may be 10 cc / min to 1000 cc / min, the carrier gas may be 10 cc / min to 1000 cc / min, the reaction gas may be 1 cc / min to 1500 cc / min, the pressure may be 0.5 Torr to 10 Torr, and the RF power may be 50 W to 1000 W or 400 W to 800 W, but is not necessarily limited thereto.

[0060] The substrate used in the method for manufacturing a metal-containing thin film according to an embodiment may be, but is not limited to, a substrate including one or more semiconductor materials selected from the group consisting of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; an SOI (Silicon On Insulator) substrate; a quartz substrate; or a glass substrate for a display; or a plastic substrate such as polyimide, polyethylene terephthalate (PET, PolyEthylene Terephthalate), polyethylene naphthalate (PEN, PolyEthylene Naphthalate), polymethyl methacrylate (PMMA, Poly Methyl MethAcrylate), polycarbonate (PC, PolyCarbonate), polyethersulfone (PES), polyester, etc.

[0061] In addition, the metal-containing thin film may be formed directly on the substrate, or multiple conductive, genetic or insulating layers may be formed between the substrate and the metal-containing thin film.

[0062] Another embodiment provides a multi-layer structure in which a metal-containing thin film is deposited on a substrate using the composition for depositing a metal-containing thin film according to an embodiment.

[0063] In one embodiment, the thin film may be an oxide film, a nitride film, an oxynitride film, a carbonitride film, or a silicon nitride film containing iodine and a metal (M), or may be a gate insulating film of a transistor or a dielectric film of a capacitor, and in particular, may be a photoresist thin film using EUV.

[0064] Examples and experimental examples are specifically illustrated below. However, the examples and experimental examples described below are merely illustrative of a part of one embodiment, and the technology described in this specification should not be construed as being limited thereto.

[0065] Example 1: Preparation of t-butylbis(dimethylamino)tin iodide [Chemical formula A] [ka] 13.0g (0.042mol) of t-butyltris(dimethylamino)tin was added to a 500mL flask, followed by 100mL of hexene, which was stirred while maintaining room temperature to produce a t-butyltris(dimethylamino)tin solution. 10.0g (0.016mol) of SnI4 was added to another 500mL flask, followed by 100mL of n-hexene, which was stirred and thoroughly diluted. The internal temperature of this solution was maintained at -10°C, and the t-butyltris(dimethylamino)tin solution prepared above was gradually added, followed by stirring at room temperature for 4 hours to synthesize t-butylbis(dimethylamino)tin iodide. After the reaction was completed, the residue was removed through a filter, and the solvent and by-products were removed under reduced pressure. Thereafter, purification was carried out at a temperature of 62° C. and a pressure of 0.5 Torr to obtain 3 g of t-butylbis(dimethylamino)iodotin.

[0066] 1 H NMR (C6D6): δ 2.66(s, 12H), δ 1.14(s, 9H)

[0067] 1 shows the TGA analysis result of t-butylbis(dimethylamino)tin iodide prepared in Example 1, which shows that the tin compound of Example 1 has a single evaporation step at about 110° C., and the residue mass at 500° C. is confirmed to be 23.4%, showing that it evaporates with rapid evaporation. As a result, it can be seen that the tin compound of Example 1 has excellent thermal stability.

[0068] Example 2: Preparation of tris(dimethylamino)tin iodide [Chemical formula B] [ka] 7.0g (0.023mol) of tetra(dimethylamino)tin was added to a 500mL flask, followed by 100mL of ether, which was stirred while maintaining room temperature to produce a tetra(dimethylamino)tin solution. 45.0g (0.008mol) of SnI was added to another 500mL flask, followed by 100mL of N-hexene, which was stirred thoroughly. The internal temperature of this solution was maintained at -10°C, and the tetra(dimethylamino)tin solution was gradually added, followed by stirring at room temperature for 4 hours to synthesize tris(dimethylamino)iodotin. After the reaction was completed, the residue was removed through a filter, and the solvent and by-products were removed under reduced pressure to obtain tris(dimethylamino)iodotin.

[0069] Thereafter, purification was carried out at a temperature of 65° C. and a pressure of 0.5 Torr to obtain 2 g of tris(dimethylamino)iodotin.

[0070] 1 H NMR (C6D6): δ 2.54(s, 18H)

[0071] 2 shows the TGA analysis results of tris(dimethylamino)tin iodine prepared in Example 2, which shows that the tin compound of Example 2 has a single evaporation step at about 120° C., and the residue mass at 500° C. is confirmed to be 25.0%, showing that it evaporates with rapid evaporation as a feature. As a result, it can be seen that the tin compound of Example 2 has excellent thermal stability.

[0072] Example 3: Preparation of bis(dimethylamino)antimony iodide [Chemical formula C] [ka] In a 500mL flask, 5.0g (0.009mol) of SbI3 was added, followed by 100mL of toluene, and then thoroughly stirred. The internal temperature of this solution was maintained at -10℃, and 5.0g (0.019mol) of tetra(dimethylamino)antimony solution was gradually added, followed by stirring at room temperature for 4 hours to synthesize bis(dimethylamino)iodine antimony. After the reaction was completed, the residue was removed through a filter, and the solvent and by-products were removed under reduced pressure to obtain 5g of bis(dimethylamino)iodine antimony.

[0073] Thereafter, purification was carried out at a temperature of 50° C. and a pressure of 0.26 Torr to obtain 2 g of tris(dimethylamino)tin iodide.

[0074] 1 H NMR (C6D6): δ 2.49(s, 12H)

[0075] 3 shows the TGA analysis results of the bis(dimethylamino)iodoantimony prepared in Example 3, which shows that the antimony compound of Example 3 has a single evaporation step at about 137° C., and the residue mass at 500° C. is confirmed to be 28.2%, showing that it evaporates with rapid evaporation as a feature. As a result, it can be seen that the antimony compound of Example 3 has excellent thermal stability.

[0076] Example 4: Preparation of bis(methylethylamino)antimony iodide [Chemical formula D] [ka] In a 500mL flask, 5.0g (0.009mol) of SbI was added, followed by 100mL of toluene, and then thoroughly stirred. The internal temperature of this solution was kept at -10℃, and 5.6g (0.02mol) of tris(methylethylamino)antimony solution was gradually added, followed by stirring at room temperature for 4 hours to synthesize bis(methylethylamino)iodine antimony. After the reaction was completed, the residue was removed through a filter, and the solvent and by-products were removed under reduced pressure to obtain 7g of bis(methylethylamino)iodine antimony.

[0077] Thereafter, purification was carried out at a temperature of 50° C. and a pressure of 0.19 Torr to obtain 2 g of bis(methylethylamino)antimony iodide.

[0078] 1 H NMR (C6D6): δ 2.36(q, 4H), δ 2.17(s, 6H), δ 0.94(t, 6H)

[0079] 4 shows the TGA analysis results of bis(methylethylamino)iodoantimony prepared in Example 4, which shows that the antimony compound of Example 4 has a single evaporation step at about 124° C., and the residue mass at 500° C. is confirmed to be 25.1%, showing that it evaporates with rapid evaporation. As a result, it can be seen that the antimony compound of Example 4 has excellent thermal stability.

[0080] <Example 5> A tin oxide thin film was prepared by plasma enhanced atomic layer deposition. The precursor was t-butylbis(dimethylamino) tin iodide prepared in Example 1, and the reactant gas was oxygen gas.

[0081] A silicon substrate was used as the substrate on which the tin oxide thin film was formed. The silicon substrate was transferred into a deposition chamber and maintained at a constant temperature as shown in Table 1 below.

[0082] The temperature of the bubbler-type canister made of stainless steel material filled with the precursor was maintained to achieve the vapor pressure of the precursor as specified in Table 1. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. Next, a purging process was performed using argon gas. A reaction process was performed using oxygen gas, which is a reactive gas, and the specified plasma power as specified in Table 1 below. In addition, a purging process was performed using argon gas to remove reaction by-products. The above-mentioned atomic layer deposition process was regarded as one cycle, and a tin oxide thin film was formed by repeating a specified cycle. The detailed evaluation conditions and results are shown in Table 1.

[0083] In addition, the composition of the tin oxide thin film was analyzed by X-ray photoelectron spectroscopy, and no carbon, nitrogen, or iodine was detected, confirming that a pure tin oxide thin film could be obtained.

[0084] [Table 1]

[0085] <Example 6> A tin oxide thin film was prepared by atomic layer deposition using t-butylbis(dimethylamino) tin iodide prepared in Example 1 as a precursor and ozone gas as a reactant gas.

[0086] A silicon substrate was used as the substrate on which the tin oxide thin film was formed, and the silicon substrate was transferred into a deposition chamber and maintained at a predetermined temperature as shown in Table 2 below.

[0087] The temperature of the bubbler-type canister made of stainless steel material filled with the precursor was maintained to achieve the vapor pressure of the specified precursor as shown in Table 2 below. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. Next, a purge process was performed using argon gas, and a reaction process was performed using ozone gas, which is a reactive gas. In addition, a purge process was performed using argon gas to remove reaction by-products. The above-mentioned atomic layer deposition process was considered as one cycle, and a tin oxide thin film was formed by repeating a predetermined cycle. The detailed evaluation conditions and results are shown in Table 2.

[0088] In addition, the composition of the tin oxide thin film was analyzed by X-ray photoelectron spectroscopy, and it was confirmed that a pure tin oxide thin film could be obtained, with no detection of carbon or nitrogen.

[0089] [Table 2]

[0090] <Example 7> A tin-containing thin film was prepared by plasma enhanced atomic layer deposition. The precursor was t-butylbis(dimethylamino)iodine tin prepared in Example 1, and the reactant gas was carbon dioxide gas.

[0091] A silicon substrate was used as the substrate on which the tin-containing thin film was formed, and the silicon substrate was transferred into a deposition chamber and maintained at a predetermined temperature as shown in Table 3 below.

[0092] The temperature of the bubbler-type canister made of stainless steel material filled with the precursor was maintained to achieve the vapor pressure of the precursor as specified in Table 3 below. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. Next, a purging process was performed using argon gas. A reaction process was performed using carbon dioxide gas, which is a reactive gas, at a plasma power as specified in Table 3 below. In addition, a purging process was performed using argon gas to remove reaction by-products. The above-mentioned atomic layer deposition process was regarded as one cycle, and a tin oxide-containing thin film was formed by repeating a specified cycle, and detailed evaluation conditions and results are shown in Table 3.

[0093] The composition of the tin-containing thin film was analyzed by X-ray photoelectron spectroscopy, and it was confirmed that the thin film contained 5 to 10% each of carbon and iodine.

[0094] [Table 3]

[0095] <Example 8> A tin-containing thin film was prepared by chemical vapor deposition using t-butylbis(dimethylamino)iodine tin prepared in Example 1 as a precursor and water vapor as a reactant gas.

[0096] A silicon substrate was used as the substrate on which the tin-containing thin film was formed, and the silicon substrate was transferred into a deposition chamber and maintained at a predetermined temperature as shown in Table 4 below.

[0097] The temperature of the bubbler-type canister made of stainless steel filled with the precursor was maintained to a predetermined vapor pressure of the precursor as shown in Table 4 below. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas. In addition, the temperature of the bubbler-type canister made of stainless steel filled with water was maintained to a predetermined vapor pressure as shown in Table 4 below, and water vapor, which is a reaction gas, was transferred into the chamber using argon gas as a carrier gas. In addition, the process pressure was adjusted using a throttle valve so that the chamber pressure was kept constant. In this way, a chemical vapor deposition method was performed using the precursor and water vapor to form a tin-containing thin film, and detailed evaluation conditions and results are shown in Table 4.

[0098] In addition, the composition of the tin-containing thin film was analyzed by X-ray photoelectron spectroscopy, and it was confirmed that the thin film contained 5 to 10% each of carbon and iodine.

[0099] [Table 4]

[0100] <Example 9> Using the tin-containing thin film produced in Example 7, patterning of the tin-containing thin film was carried out.

[0101] Approximately 76 mJ / cm2 is required for an extreme ultraviolet (EUV) lithography tool to form a 1:1 line-space pitcher with a pitch of 24 nm. 2 The film was patterned using EUV with an exposure of 100 nm, then baked at about 150° C. for 3 minutes, developed in 2-heptanone for about 15 seconds, and rinsed in the same solvent.

[0102] Figure 5 is a scanning electron microscope image of a line / space pattern formed on a silicon substrate with a pitch of 24 nm.

[0103] As shown in the pattern image, it can be seen that a 1:1 line / space pattern was formed uniformly even with a narrow pitch of 24 nm.

[0104] <Example 10> An antimony oxide thin film was prepared by plasma enhanced atomic layer deposition. The precursor was bis(methylethylamino)iodoantimony prepared in Example 4, and the reactant gas was oxygen gas.

[0105] The substrate on which the antimony oxide thin film was formed was a silicon substrate, which was transferred into a deposition chamber and maintained at a constant temperature as shown in Table 5 below.

[0106] The temperature of the bubbler-type canister made of stainless steel material filled with the precursor was maintained to achieve the vapor pressure of the precursor as specified in Table 5. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. Next, a purge process was performed using argon gas. A reaction process was performed using oxygen gas, which is a reactive gas, at a specified plasma power as specified in Table 5 below. In addition, a purge process was performed using argon gas to remove reaction by-products. The above-mentioned atomic layer deposition process was regarded as one cycle, and a predetermined cycle was repeated to form an antimony oxide thin film. The detailed evaluation conditions and results are shown in Table 5.

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

[0108] [Table 5]

[0109] <Example 11> An antimony oxide thin film was prepared by atomic layer deposition. The precursor was bis(methylethylamino) tin iodide prepared in Example 4, and the reactant gas was ozone gas.

[0110] A silicon substrate was used as the substrate on which the antimony oxide thin film was formed, and the silicon substrate was transferred into a deposition chamber and maintained at a predetermined temperature shown in Table 6 below.

[0111] The temperature of the stainless steel bubbler-type canister filled with the precursor was maintained to achieve the vapor pressure of the precursor as specified in Table 6 below. The vaporized precursor was transferred into the chamber using argon gas as a carrier gas and adsorbed onto the silicon substrate. Next, a purge process was performed using argon gas, and a reaction process was performed using ozone gas, which is a reactive gas. In addition, a purge process was performed using argon gas to remove reaction by-products. The above-mentioned atomic layer deposition process was counted as one cycle, and a predetermined cycle was repeated to form an antimony oxide thin film. The detailed evaluation conditions and results are shown in Table 6.

[0112] In addition, the composition of the antimony oxide thin film was analyzed by X-ray photoelectron spectroscopy, and no carbon or nitrogen was detected, confirming that a pure antimony oxide thin film could be obtained.

[0113] [Table 6]

[0114] Although one embodiment has been described in detail above by examples and experimental examples, the scope of one embodiment should not be limited to the specific examples, but should be interpreted by the appended claims.

Claims

1. An iodine-containing metal compound represented by the following chemical formula 2 or 3. [Chemical formula 2] 【Chemistry 2】 In the above Chemical Formula 2, M １ is Sn or Pb, R １１ is hydrogen or C １－７ is alkyl, R １２ is C １－７ is alkyl, R １３ is C １－７ Alkyl, C ２－７ Alkenyl or -NR １５ R １６ and R １４ is -NR 15 R 16, and said R １５ and R １６ are each independently hydrogen or C １－７ It may be alkyl. [Chemical formula 3] 【Chemistry 3】 In the above Chemical Formula 3, Said M ２ is Sb or Bi, The R ２１ is hydrogen or C １－７ is alkyl, The R ２２ is C １－７ is alkyl, The R ２３ is C １－７ Alkyl, C ２－７ Alkenyl or -NR ２５ R ２６ and R ２５ and R ２６ are each independently hydrogen or C １－７ It may be alkyl.

2. In the chemical formula 2, said R 11 is hydrogen or C 1-5 alkyl; said R 12 is C 1-5 alkyl; said R 13 is C 1-5 alkyl, C 2-5 alkenyl or -NR 15 R 16 ; 2. The iodine-containing metal compound according to claim 1, wherein R 14 is —NR 15 R 16 , and R 15 and R 16 may each independently be hydrogen or C 1-5 alkyl.

3. The iodine-containing metal compound according to claim 1 , wherein the compound represented by Chemical Formula 2 is any one selected from the following compound group: 【Chemistry 4】

4. In the chemical formula 2, The iodine-containing metal compound according to claim 1 , wherein M 1 is Sn.

5. The compound represented by the chemical formula 2 is or The iodine-containing metal compound according to claim 1,

6. In the chemical formula 3, said R 21 is hydrogen or C 1-5 alkyl; said R 22 is C 1-5 alkyl; 2. The iodine-containing metal compound according to claim 1, wherein R 23 is C 1-5 alkyl, C 2-5 alkenyl or -NR 25 R 26 , and R 25 and R 26 may each independently be hydrogen or C 1-5 alkyl.

7. The iodine-containing metal compound according to claim 1 , wherein the compound represented by Chemical Formula 3 is any one selected from the following compound group:

8. The compound represented by chemical formula 3 is or The iodine-containing metal compound according to claim 1,

9. In the chemical formula 3, The iodine-containing metal compound according to claim 1 , wherein M 2 is Sb.

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