Iodine-containing metal compound and composition for thin film deposition containing the same

Abstract

The present disclosure relates to an iodine-containing metal compound, a composition for depositing a metal-containing thin film including the same, and a method for manufacturing a metal-containing thin film using the same. The composition for thin film deposition according to an exemplary embodiment exists in a liquid state at room temperature, and thus is excellent in terms of storage and handling. Since it has high reactivity, a metal thin film can be effectively formed using the same.

Description

Technical Field

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

[0002] As a chemically amplified resist (CAR) which is currently used as a photoresist, it is designed for high sensitivity. However, since a general elemental structure (mainly C having smaller quantities of O, F, and S) makes the photoresist too transparent at a wavelength of 13.5 nm, a phenomenon of reduced sensitivity occurs.

[0003] In addition, it has been reported that CAR reduces process efficiency due to roughness problems in fine feature sizes, or increases line edge roughness (LER) as the photospeed decreases in a process using an acid catalyst. To solve this problem, inorganic compounds for extreme ultraviolet (EUV) lithography are required (Korean Patent Publication No. KR10-2022-0000366A). Summary of the Invention

[0004] Problems to be Solved by the Invention

[0005] One exemplary embodiment provides an iodine-containing metal compound that can be used as a precursor of a metal-containing thin film and a metal-containing thin film deposition composition containing the same.

[0006] Another exemplary embodiment provides a method for manufacturing a metal-containing thin film using the metal-containing thin film deposition composition.

[0007] Means for Solving the Problems

[0008] One exemplary embodiment provides a compound represented by the following Chemical Formula 1.

[0009] Chemical Formula 1

[0010]

[0011] In Chemical Formula 1,

[0012] M is a Group 14 metal, a Group 15 metal, or a Group 16 metal,

[0013] R 1 is hydrogen or C 1-7 alkyl,

[0014] R 2 is C 1-7 alkyl,

[0015] R 3 and R 4 are each independently C 1-7 alkyl, C 2-7 alkenyl or -NR 5 R 6 , where the R 5 and R 6 are each independently hydrogen or C 1-7 alkyl, and

[0016] According to the metal oxidation state of M, the R 3 and R 4 each independently do not exist.

[0017] Another exemplary embodiment provides a composition for depositing a metal-containing film, which contains an iodine-containing metal compound according to the above exemplary embodiment.

[0018] Another exemplary embodiment provides a method for manufacturing a metal-containing film using the composition for depositing a metal-containing film according to the above exemplary embodiment.

[0019] Advantages of the Invention

[0020] The present disclosure relates to an iodine-containing metal compound, a composition for depositing a metal-containing film containing the same, and a method for manufacturing a metal-containing film using the same. The composition for depositing a film according to an exemplary embodiment exists in a liquid state at room temperature, and thus is excellent in terms of storage and handling. Due to its high reactivity, a metal film can be effectively formed using the same. Description of the Drawings

[0021] Figure 1 Shows the thermogravimetric analysis (TGA) results of tin t-butylbis(dimethylamino)iodide prepared in Example 1.

[0022] Figure 2 Shows the TGA analysis results of tin tris(dimethylamino)iodide prepared in Example 2.

[0023] Figure 3 Shows the TGA analysis results of antimony bis(methylamino)iodide prepared in Example 3.

[0024] Figure 4 Shows the TGA analysis results of antimony bis(dimethylethylamino)iodide prepared in Example 4.

[0025] Figure 5It is a photograph of an image of a scanning electron microscope of a line / space pattern formed on a silicon substrate using the tin compound prepared in Example 1. Detailed Description of the Embodiment

[0026] Since the embodiments described in this specification can be modified in various other ways, the technology according to one exemplary embodiment is not limited to the embodiments described below. Further, unless there is a particularly contrary description, "including", "having", "containing", or "comprising" means including other constituent elements as well, rather than excluding other constituent elements, and does not exclude elements, materials, or processes not further listed.

[0027] In the numerical ranges used in this specification, all values within the lower limit value and the upper limit value are included, increments logically derived in the form and width of the defined range, all values with double limits, and all possible combinations of the upper and lower limits of the numerical ranges defined in different forms. As an example, when the content of a component 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 described in this specification. Unless otherwise defined, in this specification, values outside the numerical ranges that may be caused by experimental errors or rounding of values are also included in the defined numerical ranges.

[0028] Hereinafter, in this specification, unless otherwise specifically defined, "about" can be considered as a value within 30%, 25%, 20%, 15%, 10%, or 5% of the indicated value.

[0029] In this specification, "alkyl" refers to a straight-chain or branched-chain hydrocarbon composed only of carbon and hydrogen atoms, and may have 1 to 7, 1 to 5, or 1 to 4 carbons.

[0030] In this specification, "alkenyl" refers to a hydrocarbon having one or more carbon-carbon double bonds at any position in the chain, and may be mono-substituted or multi-substituted. For example, alkenyl may include vinyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, etc.

[0031] In this specification, a "leaving group" refers to a functional group or atom that can be substituted by a substitution reaction (e.g., a nucleophilic substitution reaction) caused by other functional groups or atoms. For example, it may be a mono-C 1-7 alkylamine or di-C 1-7 alkylamine, but is not limited thereto.

[0032] In this specification, the two alkyl groups included in "dialkylamine" may be the same or different.

[0033] One exemplary embodiment provides an iodine-containing metal compound represented by the following Chemical Formula 1.

[0034] Chemical Formula 1

[0035]

[0036] In the Chemical Formula 1,

[0037] M is a Group 14 metal, a Group 15 metal or a Group 16 metal,

[0038] R 1 is hydrogen or C 1-7 alkyl,

[0039] R 2 is C 1-7 alkyl,

[0040] R 3 and R 4 are each independently C 1-7 alkyl, C 2-7 alkenyl or -NR 5 R 6 wherein the R 5 and R 6 are each independently hydrogen or C 1-7 alkyl, and

[0041] depending on the metal oxidation state of M, the R 3 and R 4 do not exist independently.

[0042] The iodine-containing metal compound according to an embodiment can be used to prepare a metal-containing film with improved physical properties when used as a precursor for thin film deposition by introducing a monoalkylamino or dialkylamino group together into the metal. In one embodiment, the iodine-containing metal compound contains iodine and a metal, and has excellent light absorption rate and / or light emission rate for EUV, and can be effectively used as a hard mask used in a lithography process.

[0043] In one embodiment, the R 1 and R 2 can each independently be a straight-chain or branched C 1-7 alkyl, C 1-5 alkyl, C 1-4 alkyl, C 1-3 alkyl, C 1-2 alkyl or methyl.

[0044] In one embodiment, the R 3 and R 4 can each independently be a straight-chain or branched C 1-7 alkyl, C 1-6 alkyl, C 1-5 alkyl, C 1-4Alkyl, 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 Alkenyl or vinyl / ethenyl. At this time, the alkenyl includes unsaturated carbon directly connected or unsaturated carbon connected through olefin insertion. In addition, in one embodiment, the R 3 and R 4 can each independently be -NR 5 R 6 At this time, R 5 and R 6 can each independently be hydrogen or a straight-chain or branched C 1-7 alkyl, C 1-6 alkyl, C 1-5 alkyl, C 1-4 alkyl, C 1-3 alkyl, C 1-2 alkyl or methyl.

[0045] In one embodiment, the M can be Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te or Po. According to the metal oxidation state of the M, the R 3 and / or R 4 can each independently be absent.

[0046] In one embodiment, the iodine-containing metal compound can be a compound represented by the following Chemical Formula 2.

[0047] Chemical Formula 2

[0048]

[0049] In the Chemical Formula 2,

[0050] M 1 is a Group 14 metal,

[0051] R 11 is hydrogen or C 1-7 alkyl,

[0052] R 12 is C 1-7 alkyl, and

[0053] R 13 and R 14 can each independently be C 1-7 alkyl, C 2-7 alkenyl or -NR 15 R 16 The R15 and R 16 may each independently be hydrogen or a C 1-7 alkyl group.

[0054] In one embodiment, the M 1 may be Sn or Te.

[0055] In one embodiment, the R 11 and R 12 may each independently be a linear or branched C 1-7 alkyl group, a C 1-5 alkyl group, a C 1-4 alkyl group, a C 1-3 alkyl group, a C 1-2 alkyl group or a methyl group.

[0056] In one embodiment, the R 13 and R 14 may each independently be a linear or branched C 1-7 alkyl group, a C 1-6 alkyl group, a C 1-5 alkyl group, a C 1-4 alkyl group, a C 1-3 alkyl group, a C 1-2 alkyl group, a methyl group, a C 2-7 alkenyl group, a C 2-6 alkenyl group, a C 2-5 alkenyl group, a C 2-4 alkenyl group, a C 2-3 alkenyl group or a vinyl / ethenyl group. At this time, the alkenyl group includes unsaturated carbon atoms directly connected or unsaturated carbon atoms connected through olefin insertion. In addition, in one embodiment, the R 13 and R 14 may each independently be -NR 15 R 16 , at which time, R 15 and R 16 may each independently be hydrogen or a linear or branched C 1-7 alkyl group, a C 1-6 alkyl group, a C 1-5 alkyl group, a C 1-4 alkyl group, a C 1-3 alkyl group, a C 1-2 alkyl group or a methyl group.

[0057] In one embodiment, the iodine-containing metal compound may be a compound represented by Chemical Formula 3 below.

[0058] Chemical Formula 3

[0059]

[0060] In Chemical Formula 3,

[0061] M 2 is a Group 15 metal,

[0062] R 21 is hydrogen or C 1-7 alkyl,

[0063] R 22 is C 1-7 alkyl, and

[0064] R 23 is C 1-7 alkyl, C 2-7 alkenyl or -NR 25 R 26 wherein said R 25 and R 26 can each independently be hydrogen or C 1-7 alkyl.

[0065] In one embodiment, said M 2 can be Sb or Bi.

[0066] In one embodiment, said R 21 and R 22 can each independently be linear or branched C 1-7 alkyl, C 1-5 alkyl, C 1-4 alkyl, C 1-3 alkyl, C 1-2 alkyl or methyl.

[0067] In one embodiment, said R 23 can be linear or branched 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 alkenyl or vinyl / ethenyl. At this time, the alkenyl includes unsaturated carbon directly connected or unsaturated carbon connected through olefin insertion. In addition, in one embodiment, said R 23 can be -NR 25 R 26 wherein R 25 and R 26 can each independently be hydrogen or linear or branched C 1-7 alkyl, C 1-6 alkyl, C1-5 alkyl, C 1-4 alkyl, C 1-3 alkyl, C 1-2 alkyl or methyl.

[0068] In one embodiment, the compound represented by Formula 2 may be

[0069] The M 1 is a Group 14 metal, for example, it may be Sn or Te.

[0070] In one embodiment, the compound represented by Formula 3 may be

[0071] The M 2 is a Group 15 metal, for example, it may be Sb or Bi.

[0072] However, the specific compound is only an example of the compound represented by Formula 1, Formula 2 or Formula 3, and is not necessarily limited thereto.

[0073] The compound can be prepared by a possible method within the scope that can be recognized by those of ordinary skill in the art disclosed in this specification.

[0074] As a specific example, the iodine-containing metal compound represented by Formula 1 according to one embodiment can be prepared by reacting the compound of the following Formula 11 and the compound of the following Formula 12.

[0075] Formula 11

[0076]

[0077] In the Formula 11,

[0078] M is a Group 14 metal, a Group 15 metal or a Group 16 metal,

[0079] R 1 is hydrogen or C 1-7 alkyl,

[0080] R 2 is C 1-7 alkyl,

[0081] R 3 and R 4 can each independently be C 1-7 alkyl, C 2-7 alkenyl or -NR 5 R 6 The R 5 and R6 Each may independently be hydrogen or C 1-7 alkyl group,

[0082] According to the metal oxidation state of M, the R 3 and R 4 may each independently be absent, and

[0083] L is a leaving group.

[0084] Chemical formula 12

[0085] MI x

[0086] In the chemical formula 12,

[0087] M is a Group 14 metal, a Group 15 metal or a Group 16 metal,

[0088] X is selected according to the oxidation state of M and is an integer of 1 or more.

[0089] The M, R of the chemical formula 11 and the chemical formula 12 1 , R 2 , R 3 , R 4 can apply the content described for the chemical formula 1.

[0090] According to an embodiment, the method for manufacturing the iodine-containing metal compound may further include a step of purification 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 the chemical formula 1.

[0091] In one embodiment, the organic solvent may be a solvent commonly used in organic synthesis. For example, hexane, pentane, dichloromethane (DCM), dichloroethane (DCE), toluene, acetonitrile, nitromethane, tetrahydrofuran (THF), N,N-dimethylformamide (DMF) and / or N,N-dimethylacetamide (DMA) may be used.

[0092] Another embodiment provides a composition for depositing a metal-containing thin film including an iodine-containing metal compound according to an embodiment.

[0093] In one embodiment, the composition for depositing a metal-containing thin film includes an iodine-containing metal compound having a metal-iodine (M-I) bond and one or more metal-nitrogen (M-N) bonds, thereby providing the reactivity of a metal thin film deposition process using processes such as atomic layer deposition and / or chemical vapor deposition, and further improving the density and purity of the formed metal-containing thin film.

[0094] In addition, the metal-containing thin film deposition composition according to an embodiment of the present invention includes an iodine-containing metal compound having a metal and an iodine group, such that the metal-containing thin film prepared therefrom has excellent light absorption rate and light emission effect for EUV.

[0095] In one embodiment, the metal-containing thin film deposition composition exists in a liquid state at room temperature, so it is easy to store and handle, can prepare various high-purity thin films at a high deposition rate, and the thin film prepared using the metal-containing thin film deposition composition according to an embodiment has excellent durability and electrical properties, and also has excellent moisture permeability.

[0096] Another embodiment provides a method for manufacturing a metal-containing thin film using the metal-containing thin film deposition composition.

[0097] In one embodiment, any method that is feasible within the scope that can be recognized by those of ordinary skill in the art disclosed in this specification can be applied to the manufacturing method without limitation. For example, it can be performed 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).

[0098] In one embodiment, the method for manufacturing the metal-containing thin film may include the following steps: maintaining the temperature of the substrate installed in the chamber at 80°C to 400°C; bringing the iodine-containing thin film deposition composition into contact with the substrate to adsorb it onto the substrate; and injecting a reaction gas into the substrate adsorbed with the iodine-containing thin film deposition composition to form an iodine-containing thin film.

[0099] In one embodiment, the manufacturing method may further include a step of removing unreacted reactants from near the thin film by purge.

[0100] In one embodiment, the reaction gas may be oxygen, ozone, distilled water, hydrogen peroxide, nitric oxide, nitrous oxide, nitrogen dioxide, ammonia, nitrogen, hydrazine, amine, diamine, carbon monoxide, carbon dioxide, saturated or unsaturated C 1-12 hydrocarbon, hydrogen, argon, and / or helium, or a mixed gas thereof, but not limited thereto.

[0101] The manufacturing method of the metal-containing thin film according to an embodiment can adjust the deposition conditions according to the structure or thermal characteristics of the target thin film. As examples of the deposition conditions, the input flow rate of the composition for depositing the metal-containing thin film according to the embodiment, the input flow rates of the reaction gas and the transport gas, the pressure, the RF power, the substrate temperature, etc. can be mentioned. For example, the input flow rate of the composition for depositing the metal-containing thin film can be 10 cc / min to 1000 cc / min, the transport gas can be 10 cc / min to 1000 cc / min, the flow rate of the reaction gas can be 1 cc / min to 1500 cc / min, the pressure can be 0.5 torr to 10 torr, the RF power can be 50 W to 1000 W, or 400 W to 800 W, but not limited thereto.

[0102] The substrate for the manufacturing method of the metal-containing thin film according to an embodiment can be a substrate including one or more semiconductor materials among 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 plastic substrate such as polyimide, PolyEthylene Terephthalate (PET), PolyEthylene Naphthalate (PEN), Poly Methyl MethAcrylate (PMMA), PolyCarbonate (PC), Polyether Sulfone (PES), polyester, etc., but not limited thereto.

[0103] In addition, in addition to directly forming a thin film on the substrate, a plurality of conductive layers, dielectric layers, insulating layers, etc. can be formed between the substrate and the metal-containing thin film.

[0104] Another embodiment provides a multilayer structure in which a metal-containing thin film is deposited on a substrate by using the composition for depositing a metal-containing thin film according to an embodiment.

[0105] In one embodiment, the thin film can be an oxide film, a nitride film, a oxynitride film, a carbonitride film, or a silicon nitride film containing iodine and a metal (M), and can also be a gate insulating film of a transistor or a dielectric film of a capacitor. In particular, it can be a photoresist thin film using EUV.

[0106] Hereinafter, examples and experimental examples will be specifically exemplified. However, since the following examples and experimental examples are only illustrative of some embodiments, the technology described in this specification should not be construed as limited thereto.

[0107] Example 1: Preparation of t-Butylbis(dimethylamino)iodotin

[0108] Chemical formula A

[0109]

[0110] 13.0 g (0.042 mol) of t-butyltris(dimethylamino)tin was added to a 500 mL flask. Then, 100 mL of hexene was added, and the mixture was stirred at room temperature to obtain a t-butyltris(dimethylamino)tin solution. 10.0 g (0.016 mol) of SnI4 was added to another 500 mL flask. Then, 100 mL of n-hexene was added and stirred to fully dilute it. The internal temperature of this solution was maintained at -10 °C, and the prepared t-butyltris(dimethylamino)tin solution was slowly added. Then, it was stirred at room temperature for 4 hours to synthesize t-butylbis(dimethylamino)iodotin. After the reaction was completed, the residue was removed by filtration, and the solvent and by-products were removed under reduced pressure. Then, 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.

[0111] 1 H NMR (C6D6): δ2.66 (s, 12H), δ1.14 (s, 9H)

[0112] Figure 1 The TGA analysis results of the t-butylbis(dimethylamino)iodotin prepared in Example 1 are shown. From this, it can be known that the tin compound in Example 1 has a single evaporation step at about 110 °C. It was confirmed that at 500 °C, the residue mass was 23.4%, and from this, it can be known that it vaporizes in a form showing fast gasification characteristics. From this result, it can be known that the thermal stability of the tin compound in Example 1 is very excellent.

[0113] Example 2: Preparation of Tris(dimethylamino)iodotin

[0114] Chemical formula B

[0115]

[0116] 7.0 g (0.023 mol) of tris(dimethylamino)tin was added to a 500 mL flask. Subsequently, 100 mL of diethyl ether was added, and the mixture was stirred at room temperature to obtain a tris(dimethylamino)tin solution. 5.0 g (0.008 mol) of SnI4 was added to another 500 mL flask. Then, 100 mL of n-hexene was added and stirred thoroughly. The internal temperature of the solution was maintained at -10 °C, and the tris(dimethylamino)tin solution was slowly added. After that, the mixture was stirred at room temperature for 4 hours to synthesize tris(dimethylamino)iodotin. After the reaction was completed, the residue was removed by filtration, and the solvent and by-products were removed under reduced pressure to obtain tris(dimethylamino)iodotin.

[0117] After that, 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.

[0118] 1 H NMR (C6D6): δ 2.54 (s, 18H)

[0119] Figure 2 The TGA analysis results of tris(dimethylamino)iodotin prepared in Example 2 are shown. It can be seen that the tin compound in Example 2 has a single evaporation step at about 120 °C. It is confirmed that at 500 °C, the residual mass is 25.0%, indicating that it vaporizes in a form showing rapid gasification characteristics. From this result, it can be known that the thermal stability of the tin compound in Example 2 is very excellent.

[0120] Example 3: Preparation of bis(dimethylamino)iodoantimony

[0121] Chemical formula C

[0122]

[0123] 5.0 g (0.009 mol) of SbI3 was added to a 500 mL flask. Then, 100 mL of toluene was added and stirred thoroughly. The internal temperature of the solution was maintained at -10 °C, and 5.0 g (0.019 mol) of tris(dimethylamino)antimony solution was slowly added. After that, the mixture was stirred at room temperature for 4 hours to synthesize bis(dimethylamino)iodoantimony. After the reaction was completed, the residue was removed by filtration, and the solvent and by-products were removed under reduced pressure to obtain 5 g of bis(dimethylamino)iodoantimony.

[0124] After that, purification was carried out at a temperature of 50 °C and a pressure of 0.26 Torr to obtain 2 g of bis(dimethylamino)iodoantimony.

[0125] 1 1H NMR (C6D6): δ 2.49 (s, 12H)

[0126] Figure 3 The TGA analysis results of bis(dimethylamino)antimony iodide prepared in Example 3 are shown. From this, it can be seen that the antimony compound of Example 3 has a single evaporation step at about 137 °C. It is confirmed that at 500 °C, the residual mass is 28.2%, indicating that it vaporizes in a form showing rapid gasification characteristics. From this result, it can be seen that the thermal stability of the antimony compound of Example 3 is very excellent.

[0127] Example 4: Preparation of bis(methylethylamino)antimony iodide

[0128] Chemical formula D

[0129]

[0130] 5.0 g (0.009 mol) of SbI3 was added to a 500 mL flask, and then 100 mL of toluene was added and stirred well. The internal temperature of the solution was maintained at -10 °C, and 5.6 g (0.02 mol) of tris(methylethylamino)antimony solution was slowly added. Then, it was stirred at room temperature for 4 hours to synthesize bis(methylethylamino)antimony iodide. After the reaction was completed, the residue was removed by filtration, and the solvent and by-products were removed under reduced pressure to obtain 7 g of bis(methylethylamino)antimony iodide.

[0131] Subsequently, 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.

[0132] 1 1H NMR (C6D6): δ 2.36 (q, 4H), δ 2.17 (s, 6H), δ 0.94 (t, 6H)

[0133] Figure 4 The TGA analysis results of bis(methylethylamino)antimony iodide prepared in Example 4 are shown. From this, it can be seen that the antimony compound of Example 4 has a single evaporation step at about 124 °C. It is confirmed that at 500 °C, the residual mass is 25.1%, indicating that it vaporizes in a form showing rapid gasification characteristics. From this result, it can be seen that the thermal stability of the antimony compound of Example 4 is very excellent.

[0134] Example 5

[0135] Tin oxide thin films were prepared by Plasma Enhanced Atomic Layer Deposition. As a precursor, tin t-butylbis(dimethylamino)iodide prepared in Example 1 was used, and oxygen was used as the reaction gas.

[0136] A silicon substrate was used as the substrate on which the tin oxide thin film was to be formed. The silicon substrate was transferred into the deposition chamber and maintained at a constant temperature recorded in Table 1 below.

[0137] The temperature of the stainless-steel Bubbler Type canister filled with the precursor was maintained to achieve a constant precursor vapor pressure recorded in Table 1. The vaporized precursor was transferred into the chamber using argon as the carrier gas and adsorbed onto the silicon substrate. Subsequently, a purge process was performed using argon. A reaction process was performed on oxygen as the reaction gas using a constant plasma power recorded in Table 1 below. In addition, a purge process was performed using argon to remove reaction by-products. Taking the atomic layer deposition process described above as one cycle, the tin oxide thin film was formed by repeating a certain number of cycles. The detailed evaluation conditions and results are shown in Table 1.

[0138] 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.

[0139] Table 1

[0140]

[0141] Example 6

[0142] Tin oxide thin films were prepared by Atomic Layer Deposition. As a precursor, tin t-butylbis(dimethylamino)iodide prepared in Example 1 was used, and ozone was used as the reaction gas.

[0143] A silicon substrate was used as the substrate on which the tin oxide thin film was to be formed. The silicon substrate was transferred into the deposition chamber and maintained at a constant temperature recorded in Table 2 below.

[0144] The temperature of the stainless-steel canister filled with the precursor was maintained to achieve a constant precursor vapor pressure recorded in Table 2 below. The vaporized precursor was transferred into the chamber using argon as the carrier gas and adsorbed onto the silicon substrate. Subsequently, a purge process was performed using argon, and a reaction process was performed using ozone as the reaction gas. In addition, a purge process was performed using argon to remove reaction by-products. Taking the atomic layer deposition process described above as one cycle, the tin oxide thin film was formed by repeating a certain number of cycles. The detailed evaluation conditions and results are shown in Table 2.

[0145] In addition, the composition of the tin oxide thin film was analyzed by X-ray photoelectron spectroscopy, and no carbon and nitrogen were detected, confirming that a pure tin oxide thin film could be obtained.

[0146] Table 2

[0147]

[0148] Example 7

[0149] A tin-containing thin film was prepared by Plasma Enhanced Atomic Layer Deposition. As the precursor, tin t-butylbis(dimethylamino)iodide prepared in Example 1 was used, and carbon dioxide gas was used as the reaction gas.

[0150] A silicon substrate was used as the substrate on which the tin-containing thin film was to be formed. The silicon substrate was transferred into the deposition chamber and maintained at a constant temperature recorded in Table 3 below.

[0151] The temperature of the bubbler-type can made of stainless steel filled with the precursor was maintained to achieve a constant precursor vapor pressure recorded in Table 3 below. The vaporized precursor was transferred into the chamber using argon as the transfer gas and adsorbed onto the silicon substrate. Thereafter, a purge process was performed using argon. A reaction process was performed on carbon dioxide gas as the reaction gas using a constant plasma power recorded in Table 3 below. In addition, a purge process was performed using argon to remove reaction by-products. Taking the atomic layer deposition process described above as one cycle, a certain number of cycles were repeated to form a tin oxide-containing thin film. The detailed evaluation conditions and results are shown in Table 3.

[0152] In addition, the composition of the tin-containing thin film was analyzed by X-ray photoelectron spectroscopy, confirming that the thin film contained 5-10% each of carbon and iodine.

[0153] Table 3

[0154]

[0155] Example 8

[0156] A tin-containing thin film was prepared by Chemical Vapor Deposition. As the precursor, tin t-butylbis(dimethylamino)iodide prepared in Example 1 was used, and water vapor was used as the reaction gas.

[0157] A silicon substrate was used as the substrate on which the tin-containing thin film was to be formed. The silicon substrate was transferred into the deposition chamber and maintained at a constant temperature recorded in Table 4 below.

[0158] The temperature of the bubbling type tank made of stainless steel filled with the precursor is maintained so that the vapor pressure of the precursor becomes the specified vapor pressure described in Table 4 below. The vaporized precursor is transferred into the chamber using argon as the transfer gas. In addition, regarding the water vapor of the reaction gas, the temperature of the bubbling type tank made of stainless steel filled with water is maintained so that the vapor pressure becomes the constant vapor pressure described in Table 4 below, and it is transferred into the chamber using argon as the transfer gas. In addition, the process pressure is adjusted using a throttle valve so that the pressure in the chamber remains constant. As described above, chemical vapor deposition is performed using the precursor and water vapor to form a tin-containing thin film, and the detailed evaluation conditions and results are shown in Table 4.

[0159] 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 contains 5-10% of carbon and iodine (Iodine) each.

[0160] Table 4

[0161]

[0162] Example 9

[0163] Patterning of the tin-containing thin film was performed using the tin-containing thin film prepared in Example 7.

[0164] In order to form a 1:1 line-space pitch at a pitch of 24 nm, extreme ultraviolet (EUV) was used for patterning in an EUV lithography apparatus with an exposure of about 76 mJ / cm 2 . Next, it was fired at about 150 °C for 3 minutes, developed in 2-heptanone for about 15 seconds, and then rinsed with the same solvent.

[0165] Figure 5 This is a scanning electron microscope image of a line / space pattern formed on a silicon substrate at a pitch of 24 nm.

[0166] It can be seen from the image of the pattern that a uniform 1:1 line / space pattern can also be formed at a narrow pitch of 24 nm.

[0167] Example 10

[0168] An antimony oxide thin film was prepared by plasma enhanced atomic layer deposition. As the precursor, bis(methylethylamino)antimony iodide prepared in Example 4 was used, and oxygen was used as the reaction gas.

[0169] A silicon substrate was used as the substrate on which the antimony oxide thin film was to be formed. The silicon substrate was transferred into the deposition chamber and maintained at a constant temperature as described in Table 5 below.

[0170] The temperature of the stainless-steel Bubbler Type canister filled with the precursor was maintained to achieve the vapor pressure of the specified precursor as described in Table 5. The vaporized precursor was transported into the chamber using argon as the carrier gas and adsorbed onto the silicon substrate. Subsequently, a purge process was performed using argon. A reaction process was performed on oxygen as the reaction gas using the constant plasma power described in Table 5 below. In addition, a purge process was performed using argon to remove reaction by-products. The atomic layer deposition process described above was defined as one cycle, and the antimony oxide thin film was formed by repeating a certain number of cycles. The detailed evaluation conditions and results are shown in Table 5.

[0171] 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.

[0172] Table 5

[0173]

[0174]

[0175] Example 11

[0176] An antimony oxide thin film was prepared by atomic layer deposition. As the precursor, bis(methylethylamino)antimony iodide prepared in Example 4 was used, and ozone gas was used as the reaction gas.

[0177] A silicon substrate was used as the substrate on which the antimony oxide thin film was to be formed. The silicon substrate was transferred into the deposition chamber and maintained at a specified temperature as described in Table 6 below.

[0178] The temperature of the stainless-steel canister filled with the precursor was maintained to achieve a constant vapor pressure of the precursor as described in Table 6 below. The vaporized precursor was transferred into the chamber using argon as the transfer gas and adsorbed onto the silicon substrate. Subsequently, a purge process was performed using argon, and a reaction process was performed using ozone gas as the reaction gas. In addition, a purge process was performed using argon to remove reaction by-products. The atomic layer deposition process described above was defined as one cycle, and the antimony oxide thin film was formed by repeating a certain number of cycles. The detailed evaluation conditions and results are shown in Table 6.

[0179] 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.

[0180] Table 6

[0181]

[0182] As described above, an exemplary embodiment has been described in detail through examples and experimental examples. However, the scope of the exemplary embodiment is not limited to the specific examples and should be interpreted by the appended claims.

Claims

1. An iodine-containing metal compound represented by the following Chemical Formula 2 or Chemical Formula 3: Chemical Formula 2 In the Chemical Formula 2, M 1 is Sn or Pb, R 11 is hydrogen or C 1-7 alkyl group R 12 is C 1-7 alkyl R 13 is C 1-7 alkyl, C 2-7 alkenyl or -NR 15 R 16 , R 14 is -NR 15 R 16 , said R 15 and R 16 are each independently hydrogen or C 1-7 alkyl; Chemical Formula 3 In the Chemical Formula 3, M 2 is Sb, R 21 is hydrogen or C 1-7 alkyl group R 22 is C 1-7 alkyl, and R 23 is C 1-7 alkyl, C 2-7 alkenyl or -NR 25 R 26 wherein the R 25 and R 26 are each independently hydrogen or C 1-7 alkyl.

2. The iodine-containing metal compound according to claim 1, wherein The said R 11 , R 12 , R 21 and R 22 are each independently C 1-5 alkyl; and The R 13 and R 23 are each independently C 1-5 alkyl or C 2-5 alkenyl, or the R 15 , R 16 , R 25 and R 26 are each independently hydrogen or C 1-5 alkyl.

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

4. The iodine-containing metal compound according to claim 1, wherein The compound represented by the Chemical Formula 3 is any one selected from the following compound group: and 5. A composition for depositing a metal-containing thin film, characterized in that it contains the iodine-containing metal compound according to any one of claims 1 to 4.

6. A method for manufacturing a metal-containing thin film, characterized in that the iodine-containing metal compound according to any one of claims 1 to 4 is used, or a composition for depositing a metal-containing thin film containing the iodine-containing metal compound is used.

7. The method for manufacturing a metal-containing thin film according to claim 6, wherein the manufacturing method includes the following steps: maintaining the temperature of the substrate installed in the chamber at 30°C to 400°C; bringing the iodine-containing metal compound or the composition for depositing a metal-containing thin film containing the iodine-containing metal compound into contact with the substrate so that it is adsorbed onto the substrate; and injecting a reaction gas into the substrate adsorbed with the iodine-containing metal compound to form a metal-containing thin film.

8. The method for manufacturing a metal-containing thin film according to claim 7, wherein The reaction gas is selected from one or more of the group consisting of oxygen, ozone, distilled water, hydrogen peroxide, nitric oxide, nitrous oxide, nitrogen dioxide, ammonia, nitrogen, hydrazine, amine, diamine, carbon monoxide, carbon dioxide, saturated or unsaturated C 1-12 hydrocarbons, hydrogen, argon, and helium.

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