KR20230120094A - Iodine-containing metal compound and composition for thin film deposition comprising the same - Google Patents

Abstract

The present disclosure relates to a metal compound containing iodine, 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 depositing a thin film according to an embodiment exists in a liquid state at room temperature and is stored. And, since it is excellent in handling and has high reactivity, it is possible to efficiently form a metal thin film using it.

Description

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

The present disclosure relates to a metal compound containing iodine, a composition for depositing a metal-containing thin film including the same, and a method for manufacturing a metal-containing thin film using the composition for depositing a thin film.

The currently used photoresist, chemically amplified resist (CAR), is designed for high sensitivity, but its common elemental composition (mainly C, with smaller quantities of O, F, S) is 13.5 nm. At wavelengths of , a phenomenon that reduces sensitivity can occur due to making photoresists too transparent.

In addition, it has been reported that in CAR, line edge roughness (LER) increases as process efficiency decreases due to roughness issues in small feature sizes or photospeed decreases in processes using acid catalysts. In order to solve this problem, inorganic compounds for EUV (extreme ultraviolet) lithography are required (Korean Patent Publication KR10-2022-0000366A).

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

Another embodiment provides a method for manufacturing a metal-containing thin film using the composition for depositing a metal-containing thin film.

One embodiment provides a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

M is a Group 14 metal, a Group 15 metal or a Group 16 metal;

R ¹ is hydrogen or C _1-7 alkyl;

R ² is C _1-7 alkyl;

R ³ and R ⁴ are each independently C _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 alkyl; and

Depending on the metal oxidation value of M, R ³ and R ⁴ may not independently exist.

Another embodiment provides a composition for depositing a metal-containing thin film including the iodine-containing metal compound according to the embodiment.

Another embodiment provides a method for manufacturing a metal-containing thin film using the composition for depositing a metal-containing thin film according to the embodiment.

The present disclosure relates to a metal compound containing iodine, 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 depositing a thin film according to an embodiment exists in a liquid state at room temperature and is stored. And, since it is excellent in handling and has high reactivity, it is possible to efficiently form a metal thin film using it.

1 shows the results of TGA analysis of t-butylbis(dimethylamino)tin iodine prepared in Example 1.
Figure 2 shows the results of TGA analysis of tris (dimethylamino) iodine prepared in Example 2.
Figure 3 shows the results of TGA analysis of bis(methylamino)iodoantimony prepared in Example 3.
4 shows the results of TGA analysis of bis(dimethylethylamino)iodoantimony prepared in Example 4.
5 is a scanning electron microscope image of a line/space pattern formed on a silicon substrate using the tin compound prepared in Example 1. FIG.

Since the embodiments described in this specification can be modified in many different forms, the technology according to one embodiment is not limited to the embodiment described below. Furthermore, "includes", "includes", "includes", or "has" a component throughout the specification does not exclude other components unless otherwise stated, but further adds other components. It means that it may include, and does not exclude additional unlisted elements, materials or processes.

Numerical ranges, as used herein, include lower and upper limits and all values within that range, increments logically derived from the form and breadth of the range being defined, all values defined therein, and the upper and lower limits of the numerical range defined in different forms. includes all possible combinations of As an example, when the content of the composition is limited to 10% to 80% or 20% to 50%, the numerical range of 10% to 50% or 50% to 80% should also be construed as described in this specification. Unless otherwise specifically defined herein, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

Unless otherwise specified herein, "about" may be considered a value within 30%, 25%, 20%, 15%, 10% or 5% of the specified value.

As used herein, "alkyl" refers to a straight-chain or branched-chain hydrocarbon composed of only carbon and hydrogen atoms, and may have 1 to 7, 1 to 5, or 1 to 4 carbon atoms.

As used herein, "alkenyl" refers to a hydrocarbon having one or more carbon-carbon double bonds at any position in the chain, and may be monosubstituted or multisubstituted. For example, the alkenyl group may include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a butadienyl group, a pentadienyl group, a hexadienyl group, and the like.

As used herein, "leaving group" refers to a functional group or atom that can be substituted through a substitution reaction (eg, a nucleophilic substitution reaction) by another functional group or atom, for example, monoC _1-7 It may be alkylamine or diC _1-7 alkylamine, but is not limited thereto.

The two alkyl groups included in "dialkylamine" herein may be the same or different.

One embodiment provides an iodine-containing metal compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

M is a Group 14 metal, a Group 15 metal or a Group 16 metal;

R ¹ is hydrogen or C _1-7 alkyl;

R ² is C _1-7 alkyl;

R ³ and R ⁴ are each independently C _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 alkyl; and

Depending on the metal oxidation value of M, R ³ and R ⁴ may not independently exist.

An iodine-containing metal compound according to an embodiment is introduced with a monoalkylamino or dialkylamino group and an iodine group, so that a metal-containing thin film having improved physical properties can be manufactured when used as a precursor for thin film deposition. In one embodiment, the iodine-containing metal compound contains iodine and a metal and thus has excellent light absorption and/or light emission rate effects for EUV, and thus can be usefully used as a hard mask used in a photolithography process.

In one embodiment, the R ¹ and R ² are each independently straight-chain or branched-chain C _1-7 alkyl, C _1-5 alkyl, C _1-4 alkyl, C _1-3 alkyl, C _1-2 alkyl, or may be methyl.

In one embodiment, R ³ and R ⁴ are each independently linear or branched C _1-7 alkyl, C _1-6 alkyl, C _1-5 alkyl, C _1-4 alkyl, C _1-3 alkyl, Can be 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) there is. In this case, the alkenyl includes one in which an unsaturated carbon is directly connected, or an unsaturated carbon is connected through an alkylene. Also, in one embodiment, the R ³ and R ⁴ may each independently be -NR ⁵ R ⁶ , wherein R ⁵ and R ⁶ are each independently hydrogen or straight-chain 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 or methyl.

In one embodiment, the M may be Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, or Po, and depending on the metal oxidation value of M, the R ³ and/or R ⁴ may not exist independently of each other.

In one embodiment, the metal iodine compound may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2,

M ¹ is a Group 14 metal;

R ¹¹ is hydrogen or C _1-7 alkyl;

R ¹² is C _1-7 alkyl; and

R ¹³ and R ¹⁴ are each independently C _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 alkyl.

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

In one embodiment, the R ¹¹ and R ¹² are each independently straight-chain or branched-chain C _1-7 alkyl, C _1-5 alkyl, C _1-4 alkyl, C _1-3 alkyl, C _1-2 alkyl, or may be methyl.

In one embodiment, R ¹³ and R ¹⁴ are each independently linear or branched C _1-7 alkyl, C _1-6 alkyl, C _1-5 alkyl, C _1-4 alkyl, C _1-3 alkyl, Can be 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) there is. In this case, the alkenyl includes one in which an unsaturated carbon is directly connected, or an unsaturated carbon is connected through an alkylene. Also, in one embodiment, the R ¹³ and R ¹⁴ may each independently be -NR ¹⁵ R ¹⁶ , wherein R ¹⁵ and R ¹⁶ are each independently hydrogen or straight-chain 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 or methyl.

In one embodiment, the metal iodine compound may be a compound represented by Formula 3 below.

[Formula 3]

In Formula 3,

M ² is a Group 15 metal;

R ²¹ is hydrogen or C _1-7 alkyl;

R ²² is C _1-7 alkyl; and

R ²³ is C _1-7 alkyl, C _2-7 alkenyl, or -NR ²⁵ R ²⁶ , and R ²⁵ and R ²⁶ may each independently represent hydrogen or C _1-7 alkyl.

In one embodiment, the M ² may be Sb or Bi.

In one embodiment, the R ²¹ and R ²² are each independently straight-chain or branched-chain C _1-7 alkyl, C _1-5 alkyl, C _1-4 alkyl, C _1-3 alkyl, C _1-2 alkyl, or may be methyl.

In one embodiment, R ²³ is straight-chain 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 alkenyl or vinyl (ethenyl). In this case, the alkenyl includes one in which an unsaturated carbon is directly connected, or an unsaturated carbon is connected through an alkylene. Also, in one embodiment, R ²³ may be -NR ²⁵ R ²⁶ , wherein R ²⁵ and R ²⁶ are each independently hydrogen or straight-chain 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 or methyl.

In one embodiment, the compound represented by Formula 2 is , , , , , , , , , , , , , , or can be

M ¹ is a Group 14 metal, and may be, for example, Sn or Te.

In one embodiment, the compound represented by Formula 3 is , , , , , , , , , , , , , , , , , or can be

The M ² is a Group 15 metal, and may be, for example, Sb or Bi.

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

The compound may be prepared by a method possible within the scope recognized by those skilled in the art disclosed through this specification.

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

[Formula 11]

In Formula 11,

M is a Group 14 metal, a Group 15 metal or a Group 16 metal;

R ¹ is hydrogen or C _1-7 alkyl;

R ² is C _1-7 alkyl;

R ³ and R ⁴ are each independently C _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 alkyl;

Depending on the metal oxidation value of M, R ³ and R ⁴ may not independently exist; and

L is a leaving group;

[Formula 12]

MI _x

In Formula 12,

M is a Group 14 metal, a Group 15 metal or a Group 16 metal;

x is selected according to the oxidation number of M and is an integer greater than or equal to 1.

M, R ¹ , R ² , R ³ , and R ⁴ in Formulas 11 and 12 may be applied as described above with respect to Formula 1.

In the method for preparing the iodine-containing metal compound according to an embodiment, after synthesizing the iodine-containing metal compound represented by Chemical Formula 1, a temperature of about 50 ℃ to 80 ℃ or 50 ℃ to 70 ℃, and 0.1 Torr to 1.0 Torr , or a step of purifying at a pressure of 0.3 Torr to 0.8 Torr may be further included.

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, nitrile Romethane, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and/or N,N-dimethylacetamide (DMA) may be used.

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

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, such that atomic layer deposition, and/or vapor deposition, etc. It is possible to improve the reactivity of a metal thin film deposition process using the process, and further increase the density and purity of the formed metal-containing thin film.

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

In one embodiment, since the composition for depositing a metal-containing thin film is liquid at room temperature, it is easy to handle and store, and various thin films with high purity can be produced at a high deposition rate. The prepared thin film has excellent durability and electrical properties, and also has excellent moisture permeability.

Another embodiment provides a method for manufacturing a metal-containing thin film using the composition for depositing a metal-containing thin film.

In one embodiment, the manufacturing method may be applied without limitation as long as it is possible within the range recognized by those skilled in the art disclosed herein, and for example, atomic layer deposition (ALD), gas phase It may be performed by vapor deposition (CVD), metal organochemical vapor deposition (MOCVD), low pressure vapor deposition (LPCVD), plasma enhanced vapor deposition (PECVD) or polar-enhanced atomic deposition (PEALD).

In one embodiment, the manufacturing method of the metal-containing thin film may include the following steps:

maintaining the temperature of the substrate mounted in the chamber at 80 °C to 400 °C;

contacting the substrate with the iodine-containing thin film deposition composition and adsorbing it onto the substrate; and

Forming an iodine-containing thin film by injecting a reaction gas into the substrate to which the iodine-containing thin film deposition composition is adsorbed.

In one embodiment, the manufacturing method may further include a step of purging to remove unreacted reactants from the vicinity of the formed thin film.

In one embodiment, the reaction gas is oxygen, ozone, distilled water, hydrogen peroxide, nitrogen monoxide, nitrous oxide, nitrogen dioxide, ammonia, nitrogen, hydrazine, amines, diamines, carbon monoxide, carbon dioxide, saturated or unsaturated C _1-12 hydrocarbons, hydrogen , argon and/or helium, or a mixed gas thereof, but is not necessarily limited thereto.

In the method for manufacturing a metal-containing thin film according to an embodiment, deposition conditions may be adjusted according to the structure or thermal characteristics of the desired thin film, and an example of the deposition condition is the input flow rate of the composition for depositing a metal-containing thin film according to the embodiment. , reaction gas, input flow rate of carrier gas, pressure, RF power, substrate temperature, etc. may be exemplified. For example, the input flow rate of the metal-containing thin film deposition composition is 10 cc/min to 1000 cc/min, the carrier gas is 10 cc/min to 1000 cc/min, and the reaction gas flow rate is 1 cc/min to 1500 cc/min. min, the pressure may be 05 torr to 10 torr, the RF power may be 50 W to 1000 W, or 400 W to 800 W, but is not necessarily limited thereto.

A substrate used in a method of manufacturing a metal-containing thin film according to an embodiment includes a substrate including at least one semiconductor material selected from among Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; SOI (Silicon On Insulator) substrate; quartz substrate; Or a glass substrate for a display; Polyimide, Polyethylene Terephthalate (PET), PolyEthylene Naphthalate (PEN), Poly Methyl Methacrylate (PMMA), Polycarbonate (PC, PolyCarbonate), Polyethersulfone (PES), a plastic substrate such as polyester (Polyester); It may be, but is not limited thereto.

In addition to directly forming the metal-containing thin film on the substrate, a plurality of conductive layers, dielectric layers, or insulating layers may be formed between the substrate and the metal-containing thin film.

Another embodiment provides a multilayer 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.

In one embodiment, the thin film may be an oxide film, nitride film, oxynitride film, carbon nitride film, or silicon nitride film containing iodine and metal (M), or may be a gate insulating film of a transistor or a dielectric film of a capacitor. It may be a resist thin film.

Hereinafter, Examples and Experimental Examples will be specifically exemplified and described. However, since the following examples and experimental examples are merely illustrative of a part of one implementation, the technology described in this specification should not be construed as being limited thereto.

<Example 1> Preparation of t-butylbis(dimethylamino)iodine tin

[Formula A]

After adding 13.0 g (0.042 mol) of t-butyltris(dimethylamino)tin to a 500mL flask and then adding 100mL of hexene, stirring while maintaining room temperature, the t-butyltris(dimethylamino)tin solution was manufactured. 10.0 g (0.016 mol) of SnI ₄ was added to another 500 mL flask, followed by addition of 100 mL of n-hexene, followed by stirring to sufficiently dilute the mixture. While maintaining the internal temperature of this solution at -10 ° C, the prepared t-butyltris (dimethylamino) tin solution was slowly added and stirred at room temperature for 4 hours to synthesize t-butylbis (dimethylamino) iodine tin did After completion of the reaction, the residue was removed through a filter and the solvent and by-products were removed under reduced pressure. Thereafter, 3 g of t-butylbis(dimethylamino)iodotin was obtained by purification under a temperature of 62 °C and a pressure of 0.5 Torr.

¹ H NMR (C ₆ D ₆ ): δ 2.66 (s, 12H), δ 1.14 (s, 9H)

1 shows the TGA analysis results of t-butylbis(dimethylamino)tin iodine prepared in Example 1, from which it can be seen that the tin compound of Example 1 has a single evaporation step at about 110 ° C. , the residue mass at 500 °C was confirmed to be 23.4%, indicating rapid vaporization and vaporization. From these results, it can be seen that the tin compound of Example 1 has excellent thermal stability.

<Example 2> Preparation of tris (dimethylamino) iodine tin

[Formula B]

7.0 g (0.023 mol) of tetra(dimethylamino)tin was added to a 500mL flask, and then 100mL of ether was added and stirred while maintaining room temperature to prepare a tetra(dimethylamino)tin solution. 5.0 g (0.008 mol) of SnI ₄ was added to another 500 mL flask, followed by 100 mL of n-hexene, followed by sufficient stirring. While maintaining the internal temperature of this solution at -10 °C, a tetra(dimethylamino)tin solution was slowly added thereto, followed by stirring at room temperature for 4 hours to synthesize tris(dimethylamino)tin iodine. After completion of the reaction, the residue was removed through a filter and the solvent and by-products were removed under reduced pressure to obtain tris(dimethylamino)iodotin.

Thereafter, 2 g of tris(dimethylamino)iodotin was obtained by purification under a temperature of 65° C. and a pressure of 0.5 Torr.

¹ H NMR (C ₆ D ₆ ): δ 2.54 (s, 18H)

2 shows the results of TGA analysis of tris(dimethylamino)tin iodine prepared in Example 2, from which it can be seen that the tin compound of Example 2 has a single evaporation step at about 120 ° C, and 500 ° C It can be seen that the residue mass is 25.0% in , which shows the characteristics of rapid vaporization and vaporization. From these results, it can be seen that the tin compound of Example 2 has excellent thermal stability.

<Example 3> Preparation of bis(dimethylamino)iodoantimony

[Formula C]

5.0 g (0.009 mol) of SbI ₃ was added to a 500 mL flask, followed by 100 mL of toluene, followed by sufficient stirring. While maintaining the internal temperature of this solution at -10 °C, a solution of 5.0 g (0.019 mol) of tetra(dimethylamino)antimony was slowly added thereto, and then stirred at room temperature for 4 hours to synthesize bis(dimethylamino)iodoantimony. After completion of the reaction, the residue was removed through a filter and the solvent and by-products were removed under reduced pressure to obtain 5 g of bis(dimethylamino)iodoantimony.

Thereafter, 2 g of tris(dimethylamino)iodoantimony was obtained by purification under a temperature of 50° C. and a pressure of 0.26 Torr.

¹ H NMR (C ₆ D ₆ ): δ 2.49 (s, 12H)

3 shows the TGA analysis results of bis(dimethylamino)iodoantimony prepared in Example 3, from which it can be seen that the antimony compound of Example 3 has a single evaporation step at about 137 ° C., At 500 °C, the residue mass was confirmed to be 28.2%, indicating rapid vaporization and vaporization. From these results, it can be seen that the antimony compound of Example 3 has excellent thermal stability.

<Example 4> Preparation of bis(methylethylamino)iodoantimony

[Formula D]

5.0 g (0.009 mol) of SbI ₃ was added to a 500 mL flask, followed by 100 mL of toluene, followed by sufficient stirring. While maintaining the internal temperature of this solution at -10 ° C, a solution of 5.6 g (0.02 mol) of tris (methylethylamino) antimony was gradually added thereto, and stirred at room temperature for 4 hours to synthesize bis (methylethylamino) iodine antimony. After completion of the reaction, the residue was removed through a filter, and then the solvent and by-products were removed under reduced pressure to obtain 7 g of bis(methylethylamino)iodoantimony.

Thereafter, 2 g of bis(methylethylamino)iodoantimony was obtained by purification under a temperature of 50° C. and a pressure of 0.19 Torr.

¹ H NMR (C ₆ D ₆ ): δ 2.36 (q, 4H), δ 2.17 (s, 6H), δ 0.94 (t, 6H)

4 shows the TGA analysis results of bis(methylethylamino)iodoantimony prepared in Example 4, from which it can be seen that the antimony compound of Example 4 has a single evaporation step at about 124 ° C., At 500 °C, the residue mass was confirmed to be 25.1%, indicating rapid vaporization and vaporization. From these results, it can be seen that the antimony compound of Example 4 has excellent thermal stability.

<Example 5>

A tin oxide thin film was prepared by plasma enhanced atomic layer deposition. As a precursor, t-butylbis(dimethylamino)tin iodine prepared in Example 1 was used, and oxygen gas was used as a reaction gas.

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

The temperature of the bubbler-type canister made of stainless steel filled with the precursor was maintained at a constant vapor pressure of the precursor shown in Table 1. The vaporized precursor was transferred into the chamber using argon gas as a transfer gas and adsorbed onto the silicon substrate. Then, a purge process was performed using argon gas. The reaction process was carried out using oxygen gas as a reaction gas at a constant plasma power shown in Table 1 below. In addition, a purge process was performed using argon gas to remove reaction by-products. A tin oxide thin film was formed by repeating a certain cycle with the above atomic layer deposition process as one cycle, and detailed evaluation conditions and results are shown in Table 1.

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 because carbon, nitrogen, and iodine were not detected.

precursor Board
temperature precursor
vapor pressure precursor injection Fudge reaction Fudge to give deposition
speed argon
bubble hour argon hour Oxygen plasma
Power hour argon hour [℃] [Torr] [sccm] [sec] [sccm] [sec] [sccm] [W] [sec] [sccm] [sec] [No.] [Å/cycle] Example 1 room temperature 0.1 100 3 600 5 600 400 3 600 5 500 1.27 100 0.1 100 3 600 5 600 400 3 600 5 500 1.17 200 0.1 100 3 600 5 600 400 3 600 5 500 1.23 400 0.1 100 3 600 5 600 400 3 600 5 500 1.45 100 0.1 100 3 600 5 600 5 3 600 5 500 0.82 100 0.1 100 3 600 5 600 50 3 600 5 500 1.06 100 0.1 100 3 600 5 600 100 3 600 5 500 1.15 100 0.1 100 3 600 5 600 400 3 600 5 500 1.17 100 0.1 100 3 600 5 600 800 3 600 5 500 1.23

<Example 6>

A tin oxide thin film was prepared by atomic layer deposition. As a precursor, t-butylbis(dimethylamino)tin iodine prepared in Example 1 was used, and ozone gas was used as a reaction gas.

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

The temperature of the bubbler-type canister made of stainless steel filled with the precursor was maintained at a constant vapor pressure of the precursor shown in Table 2 below. The vaporized precursor was transferred into the chamber using argon gas as a transfer gas and adsorbed onto the silicon substrate. Thereafter, a purge process was performed using argon gas, and a reaction process was performed using ozone gas as a reaction gas. In addition, a purge process was performed using argon gas to remove reaction by-products. A tin oxide thin film was formed by repeating a certain cycle with the above atomic layer deposition process as one cycle, and detailed evaluation conditions and results are shown in Table 2.

In addition, the composition of the tin oxide thin film was analyzed through X-ray photoelectron spectroscopy, and it was confirmed that a pure tin oxide thin film could be obtained because carbon and nitrogen were not detected.

precursor Board
temperature precursor
vapor pressure precursor injection Fudge reaction Fudge to give deposition
speed argon
bubble hour argon hour ozone ozone concentration hour argon hour [℃] [Torr] [sccm] [sec] [sccm] [sec] [sccm] [g/m³] [sec] [sccm] [sec] [No.] [Å/cycle] Example 1 room temperature 0.1 100 3 600 5 600 220 3 600 5 500 1.23 100 0.1 100 3 600 5 600 220 3 600 5 500 1.10 200 0.1 100 3 600 5 600 220 3 600 5 500 1.17 400 0.1 100 3 600 5 600 220 3 600 5 500 1.43

<Example 7>

A tin-containing thin film was prepared by plasma enhanced atomic layer deposition. As a precursor, t-butylbis(dimethylamino)tin iodine prepared in Example 1 was used, and carbon dioxide gas was used as a reaction gas.

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

The temperature of the bubbler-type canister made of stainless steel filled with the precursor was maintained at a constant vapor pressure of the precursor shown in Table 3 below. The vaporized precursor was transferred into the chamber using argon gas as a transport gas and adsorbed onto the silicon substrate. Then, a purge process was performed using argon gas. The reaction process was carried out using carbon dioxide gas as a reaction gas at a constant plasma power shown in Table 3 below. In addition, a purge process was performed using argon gas to remove reaction by-products. A tin oxide-containing thin film was formed by repeating the above atomic layer deposition process as one cycle, and the detailed evaluation conditions and results are shown in Table 3.

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

precursor Board
temperature precursor
vapor pressure precursor injection Fudge reaction Fudge to give deposition
speed argon
bubble hour argon hour Dioxide
carbon plasma
Power hour argon hour [℃] [Torr] [sccm] [sec] [sccm] [sec] [sccm] [W] [sec] [sccm] [sec] [No.] [Å/cycle] Example 1 room temperature 0.1 100 3 600 3 600 50 2 600 3 500 1.02 100 0.1 100 3 600 3 600 50 2 600 3 500 0.94 200 0.1 100 3 600 3 600 50 2 600 3 500 0.98 400 0.1 100 3 600 3 600 50 2 600 3 500 1.20 100 0.1 100 3 600 3 600 5 2 600 3 500 0.75 100 0.1 100 3 600 3 600 50 2 600 3 500 0.94 100 0.1 100 3 600 3 600 100 2 600 3 500 0.98 100 0.1 100 3 600 3 600 400 2 600 3 500 1.00 100 0.1 100 3 600 3 600 800 2 600 3 500 1.05

<Example 8>

A tin-containing thin film was prepared by chemical vapor deposition. As a precursor, t-butylbis(dimethylamino)tin iodine prepared in Example 1 was used, and water vapor was used as a reaction gas.

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

The temperature of the bubbler-type canister made of stainless steel filled with the precursor was maintained at a constant vapor pressure of the precursor shown in Table 4 below. The vaporized precursor was transferred into the chamber using argon gas as a transport gas. In addition, water vapor, which is a reaction gas, was transferred into a chamber using argon gas as a transport gas while maintaining a temperature such that a water-filled bubbler-type canister made of stainless steel had a constant vapor pressure as shown in Table 4 below. In addition, the process pressure was adjusted using a throttle valve so that the pressure in the chamber was kept constant. As such, 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.

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

precursor Board
temperature precursor water transport gas
argon process pressure deposition
hour deposition
speed vapor pressure argon
bubble vapor pressure argon
bubble [℃] [Torr] [sccm] [Torr] [sccm] [sccm] [Torr] [min] [Å/min] Example 1 70 0.1 100 6 10 600 One 10 42 70 0.1 100 6 10 600 2 10 48 70 0.1 100 6 10 600 3 10 50 room temperature 0.1 100 6 10 600 2 10 85 70 0.1 100 6 10 600 2 10 48 200 0.1 100 6 10 600 2 10 43 400 0.1 100 6 10 600 2 10 52

<Example 9>

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

It was patterned using EUV with an exposure of about 76 mJ/cm ² in extreme ultraviolet (EUV) lithography equipment to form 1:1 line-space features at a pitch of 24 nm. It was then calcined at about 150° C. for 3 minutes, developed in 2-heptanone for about 15 seconds, and then rinsed with the same solvent.

5 is a scanning electron microscope image of a line/space pattern formed on a silicon substrate at pitches of 24 nm.

As can be seen in the image of the pattern, it can be confirmed that the 1:1 line/space pattern is evenly formed even at a narrow pitch of 24 nm.

<Example 10>

An antimony oxide thin film was prepared by plasma enhanced atomic layer deposition. Bis(methylethylamino)iodoantimony prepared in Example 4 was used as a precursor, and oxygen gas was used as a reaction gas.

A silicon substrate was used as a substrate on which the antimony oxide thin film was formed, and the silicon substrate was transferred into a deposition chamber and kept constant at a temperature shown in Table 5 below.

The temperature of the bubbler-type canister made of stainless steel filled with the precursor was maintained at a constant vapor pressure of the precursor shown in Table 5. The vaporized precursor was transferred into the chamber using argon gas as a transport gas and adsorbed onto the silicon substrate. Then, a purge process was performed using argon gas. The reaction process was performed using oxygen gas as a reaction gas at a constant plasma power shown in Table 5 below. In addition, a purge process was performed using argon gas to remove reaction by-products. The above atomic layer deposition process was set as one cycle to form an antimony oxide thin film by repeating a certain cycle, and detailed evaluation conditions and results are shown in Table 5.

In addition, the composition of the antimony oxide thin film was analyzed through X-ray photoelectron spectroscopy, and it was confirmed that a pure antimony oxide thin film could be obtained because carbon, nitrogen, and iodine were not detected.

precursor Board
temperature precursor
vapor pressure precursor injection Fudge reaction Fudge to give deposition
speed argon
bubble hour argon hour Oxygen plasma
Power hour argon hour [℃] [Torr] [sccm] [sec] [sccm] [sec] [sccm] [W] [sec] [sccm] [sec] [No.] [Å/cycle] Example 4 room temperature 0.1 100 3 600 5 600 400 3 600 5 500 1.41 100 0.1 100 3 600 5 600 400 3 600 5 500 1.30 200 0.1 100 3 600 5 600 400 3 600 5 500 1.32 400 0.1 100 3 600 5 600 400 3 600 5 500 1.59 100 0.1 100 3 600 5 600 5 3 600 5 500 0.91 100 0.1 100 3 600 5 600 50 3 600 5 500 1.15 100 0.1 100 3 600 5 600 100 3 600 5 500 1.21 100 0.1 100 3 600 5 600 400 3 600 5 500 1.30 100 0.1 100 3 600 5 600 800 3 600 5 500 1.35

<Example 11>

An antimony oxide thin film was prepared by atomic layer deposition. Bis(methylethylamino)iodoantimony prepared in Example 4 was used as a precursor, and ozone gas was used as a reaction gas.

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

The temperature of the bubbler-type canister made of stainless steel filled with the precursor was maintained at a constant vapor pressure of the precursor shown in Table 6 below. The vaporized precursor was transferred into the chamber using argon gas as a transport gas and adsorbed onto the silicon substrate. Thereafter, a purge process was performed using argon gas, and a reaction process was performed using ozone gas as a reaction gas. In addition, a purge process was performed using argon gas to remove reaction by-products. The above atomic layer deposition process was set as one cycle to form an antimony oxide thin film by repeating a certain cycle, and detailed evaluation conditions and results are shown in Table 6.

In addition, the composition of the antimony oxide thin film was analyzed through X-ray photoelectron spectroscopy, and it was confirmed that a pure antimony oxide thin film could be obtained because carbon and nitrogen were not detected.

precursor Board
temperature precursor
vapor pressure precursor injection Fudge reaction Fudge to give deposition
speed argon
bubble hour argon hour ozone ozone concentration hour argon hour [℃] [Torr] [sccm] [sec] [sccm] [sec] [sccm] [g/m³] [sec] [sccm] [sec] [No.] [Å/cycle] Example 4 room temperature 0.1 100 3 600 5 600 220 3 600 5 500 1.45 100 0.1 100 3 600 5 600 220 3 600 5 500 1.21 200 0.1 100 3 600 5 600 220 3 600 5 500 1.31 400 0.1 100 3 600 5 600 220 3 600 5 500 1.61

In the above, an embodiment has been described in detail through Examples and Experimental Examples, but the scope of an embodiment is not limited to a specific embodiment, and should be interpreted according to the appended claims.

Claims (10)

An iodine-containing metal compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
M is a Group 14 metal, a Group 15 metal or a Group 16 metal;
R ¹ is hydrogen or C _1-7 alkyl;
R ² is C _1-7 alkyl;
R ³ and R ⁴ are each independently C _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 alkyl; and
Depending on the metal oxidation value of M, R ³ and R ⁴ may not independently exist. According to claim 1,
Wherein R ¹ and R ² are each independently C _1-5 alkyl;
R ³ and R ⁴ are each independently C _1-5 alkyl, C _2-5 alkenyl or -NR ⁵ R ⁶ , R ⁵ and R ⁶ are each independently hydrogen or C _1-5 alkyl; and
Depending on the metal oxidation value of M, the R ³ and R ⁴ may not each independently exist, an iodine-containing metal compound. According to claim 1,
The iodine-containing metal compound is an iodine-containing metal compound represented by Formula 2 or Formula 3 below:
[Formula 2]

In Formula 2,
M ¹ is a Group 14 metal;
R ¹¹ is hydrogen or C _1-7 alkyl;
R ¹² is C _1-7 alkyl; and
R ¹³ and R ¹⁴ are each independently C _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 alkyl;
[Formula 3]

In Formula 3,
M ² is a Group 15 metal;
R ²¹ is hydrogen or C _1-7 alkyl;
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 R ²⁵ and R ²⁶ are each independently hydrogen or C _1-7 alkyl. According to claim 3,
R ¹¹ , R ¹² , R ²¹ and R ²² are each independently C _1-5 alkyl; and
Wherein R ¹³ , R ¹⁴ and R ²³ are each independently C _1-5 alkyl or C _2-5 alkenyl, or R ¹⁵ , R ¹⁶ , R ²⁵ and R ²⁶ are each independently hydrogen or C _1-5 Alkyline, an iodine-containing metal compound. According to claim 3,
The compound represented by Formula 2 is any one selected from the following compound group, an iodine metal compound:
, , , , , , , , , , , , , , and . According to claim 3,
The compound represented by Formula 3 is any one selected from the following compound group, an iodine metal compound:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

and

. A composition for depositing a metal-containing thin film comprising the iodine-containing metal compound according to any one of claims 1 to 6. A method of manufacturing a metal-containing thin film using the iodine-containing metal compound according to any one of claims 1 to 6 or a composition for depositing a metal-containing thin film including the same. According to claim 8,
The method for producing a metal-containing thin film comprising the following steps:
maintaining the temperature of the substrate mounted in the chamber at 30 °C to 400 °C;
contacting the iodine-containing metal compound or the composition for depositing a metal-containing thin film including the iodine-containing metal compound on a substrate and adsorbing the iodine-containing compound onto the substrate; and
Forming a metal-containing thin film by injecting a reaction gas into the substrate on which the iodine-containing metal compound is adsorbed. According to claim 9,
The reaction gas is oxygen, ozone, distilled water, hydrogen peroxide, nitrogen monoxide, nitrous oxide, nitrogen dioxide, ammonia, nitrogen, hydrazine, amines, diamines, carbon monoxide, carbon dioxide, saturated or unsaturated C _1-12 hydrocarbons, hydrogen, argon and helium. Any one or more selected from the group consisting of, a method for producing a metal-containing thin film.