Selective deposition method of thin film using area-selective atomic layer deposition and substrate on which thin film is selectively formed

Abstract

The present invention relates to a method for selectively depositing a thin film using area-selective atomic layer deposition and a substrate on which a thin film is selectively formed, and more particularly, to a method for selectively depositing a thin film using area-selective atomic layer deposition, in which thin films having different thicknesses are formed on the surface of a substrate containing a metal such as copper (Cu), a substrate containing silicon dioxide (SiO2), and a substrate containing a nitride similar to titanium nitride (TiN), using an organic thiol small molecule inhibitor, and a substrate on which a thin film is selectively formed.

Description

[Technical Field]

[0001] The present invention relates to a method for selectively depositing a thin film using area-selective atomic layer deposition and a substrate on which the thin film is selectively formed. More specifically, the present invention relates to a method for selectively depositing a thin film using area-selective atomic layer deposition, in which the surfaces of three or more substrates, i.e., a metal-containing substrate, a silicon dioxide (SiO2)-containing substrate, and a nitride-containing substrate, are passivated using an organic thiol small molecule inhibitor to form thin films having different thicknesses, and a substrate on which the thin film is selectively formed. [Background technology]

[0002] As the technology in the semiconductor industry advances, the size of semiconductor devices continues to shrink to meet the demands of the semiconductor market, currently requiring sizes of less than 10 nm.

[0003] Therefore, existing top-down semiconductor device manufacturing methods, which involve repetitive lithography and etching processes, have reached physical limits in manufacturing semiconductor devices at the 10nm level or below. For example, device performance and reliability are reduced due to inaccurate device patterning and misalignment of patterned features during device layering.

[0004] Atomic layer deposition (ALD) is a thin film deposition technology that offers significant advantages over other thin film deposition methods in terms of uniformity, thickness control, and conformality.

[0005] The self-limiting surface characteristics of the atomic layer deposition process offer additional benefits in addition to thin film deposition and area selective deposition (ASD). Specifically, localized deposition can be achieved through area selective deposition by controlling the surface chemical reactivity in a vacuum environment using appropriate chemical treatments. This area selective deposition allows for upward transfer by applying an appropriate pattern to the original surface, eliminating the need for repetitive lithography and etching processes. It can also be used to create additional patterns within 3D patterns, which is not possible with existing technology. This also has the advantage of minimizing side effects that can occur in current complex processes, thereby reducing manufacturing costs.

[0006] Area-selective atomic layer deposition (AS-ALD) is one of the most reliable deposition methods among atomic layer deposition (ALD). Furthermore, using an inhibitor in AS-ALD is an effective method for surface functionalization. Inhibitors are selectively adsorbed onto the surface, causing passivation during ALD, thereby inducing selective area inactivation. Conventional inhibitors include SAMs (self-assembled monolayers), SMIs (small molecule inhibitors), and PISs (precursor inhibitors).

[0007] SAMs are self-assembling molecules that can be adsorbed with surface sensitivity and surface selectivity to inhibit growth. However, as the size of semiconductor devices continues to shrink, there are physical limitations to using SAMs with a certain size due to their low thermal stability.

[0008] SMIs are generally nanometer-sized molecules with characteristic chemisorption reaction regions and have similar adsorption selectivity to SAMs. This adsorption selectivity is determined by the inert ligand. Utilizing nanometer-sized SMIs in area selective deposition (ASD) can overcome the difficulties of high-volume manufacturing that SAMs face. Furthermore, SMIs do not require the adsorption process that SAMs must undergo in wet chemical processes. Consequently, SMIs are being proposed as a better inhibitor than SAMs, which have been widely used in the past. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention aims to provide a method for selectively depositing a thin film using area-selective atomic layer deposition (ALD), which uses an organic thiol small molecule inhibitor that has surface sensitivity and surface selectivity like a SAM and is adsorbed onto the surface of a substrate, thereby providing excellent vapor pressure, easy chamber transfer, and the ability to form a dense layer in a short time, as well as a substrate on which a thin film is selectively formed.

[0010] Another object of the present invention is to provide a method for selectively depositing a thin film using area-selective atomic layer deposition, which forms thin films with different thicknesses on the surfaces of a metal-containing substrate, a silicon dioxide (SiO2)-containing substrate, and a nitride-containing substrate by using an organic thiol small molecule inhibitor that is adsorbed at different concentrations on the surfaces of a metal-containing substrate, a silicon dioxide (SiO2)-containing substrate, and a nitride-containing substrate, and to provide a substrate on which a thin film is selectively formed. [Means for solving the problem]

[0011] To achieve the above object, a method for selectively depositing a thin film using area-selective atomic layer deposition (AS-ALD) according to the present invention includes the following steps: (1) preparing a substrate in which a first substrate containing a metal, a second substrate containing silicon dioxide (SiO), and a third substrate containing a nitride are arranged in parallel; (2) exposing the substrate to an organic thiol small molecule inhibitor; and (3) forming a thin film on the surface of the substrate exposed to the organic thiol small molecule inhibitor using area-selective atomic layer deposition (AS-ALD). The metal of the first substrate according to the present invention may be selected from the group consisting of copper (Cu), cobalt (Co), ruthenium (Ru), molybdenum (Mo), and tungsten (W), preferably copper (Cu). The nitride of the third substrate according to the present invention may be selected from the group consisting of titanium nitride, molybdenum nitride, tungsten nitride, and silicon nitride, preferably titanium nitride. The thin film formed by the present invention may be a thin film selected from the group consisting of metals, metal oxides, and silicon dielectric materials, and is preferably a hafnium oxide (HfO2) thin film.

[0012] In a preferred embodiment of the present invention, the thickness of the thin film formed on the surface of the first substrate, the thickness of the thin film formed on the surface of the second substrate, and the thickness of the thin film formed on the surface of the third substrate may be different.

[0013] In a preferred embodiment of the present invention, the method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention can satisfy the following condition (1):

[0014] (1) A <B<C

[0015] In the above condition (1), A represents the thickness of the thin film formed on the surface of the first substrate, B represents the thickness of the thin film formed on the surface of the second substrate, and C represents the thickness of the thin film formed on the surface of the third substrate.

[0016] In a preferred embodiment of the present invention, the organic thiol small molecule inhibitor may include a compound represented by the following Chemical Formula 1:

[0017] [ka]

[0018] In the above formula 1, R 1 and R 2 are each independently a C1 to C12 linear alkyl group, a C3 to C12 branched alkyl group, or a C6 to C12 aryl group. 1 and R 2 is a C1 to C12 linear alkyl group, more preferably a C1 to C3 linear alkyl group.

[0019] In a preferred embodiment of the present invention, the second step of the method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention includes: Step 2-1 of drying the substrate and then placing it in a chamber having an internal temperature of about 300°C to about 500°C and a vacuum base pressure condition, and maintaining the chamber for about 1 to about 20 minutes; Step 2-2 of purging the chamber and maintaining the internal temperature of the chamber at about 200°C to about 500°C, introducing an organic thiol small molecule inhibitor into the chamber, and exposing the substrate to the organic thiol small molecule inhibitor for about 1 to about 100 seconds; and Step 2-3 of cooling the substrate exposed to the organic thiol small molecule inhibitor to a temperature of about 15°C to about 35°C.

[0020] In a preferred embodiment of the present invention, in the second step of the selective deposition method for a thin film using area-selective atomic layer deposition of the present invention, the surface of the first substrate exposed to the organic thiol small molecule inhibitor may have a water contact angle of about 90° to about 100°, and the surface of the second substrate exposed to the organic thiol small molecule inhibitor may have a water contact angle of about 70° to about 80°.

[0021] In a preferred embodiment of the present invention, in the second step of the selective deposition method for a thin film using area-selective atomic layer deposition of the present invention, the organic thiol small molecule inhibitor introduced into the chamber is thermally dissociated into an alkylsulfanyl and an alkyl, and the alkylsulfanyl is adsorbed on the surface of the first substrate, and the alkyl is adsorbed on the surface of the second substrate. In this case, the alkylsulfanyl is preferably ethylsulfanyl, and the alkyl is preferably ethyl.

[0022] In a preferred embodiment of the present invention, the third step of the method for selectively depositing a thin film using region-selective atomic layer deposition of the present invention includes step 3-1 of placing a substrate exposed to an organic thiol small molecule inhibitor into a chamber and heating it to about 200°C to about 350°C, and step 3-2 of performing region-selective atomic layer deposition in cycles of placing a precursor for thin film deposition into the chamber, exposing it for about 1 second to about 10 seconds, and purging it for about 50 seconds to about 70 seconds, and placing a reactant into the chamber, exposing it for about 1 second to about 5 seconds, and purging it for about 50 seconds to about 70 seconds.

[0023] In a preferred embodiment of the present invention, the precursor for thin film deposition may be a volatile precursor containing a Group 3 to Group 16 compound such as a titanium compound, a hafnium compound, a zirconium compound, a tantalum compound, a vanadium compound, a niobium compound, a molybdenum compound, or a silicon compound.

[0024] In a preferred embodiment of the present invention, the precursor for thin film deposition may include at least one compound selected from the group consisting of a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, a compound represented by the following Chemical Formula 4, and a compound represented by the following Chemical Formula 5:

[0025] [Chemical formula 2] (L1) nM(NR 3 R 4 ) 4-n

[0026] In the above formula 2, L1 is a ligand selected from the group consisting of cyclopentadienyl and C1-C12 alkyl-substituted cyclopentadienyl, M is a metal selected from the group consisting of titanium, hafnium, and zirconium, and R 3 and R 4 are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group; and n is 0, 1, or 2.

[0027] [Chemical formula 3] R 5 m M(OR 6 ) 3-m

[0028] In the formula 3, M is a metal selected from the group consisting of aluminum, hafnium, and zirconium; R 5 and R 6 are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and m is 1 to 3.

[0029] [Chemical formula 4] (L2) p MR 7 (OR 8 ) 3-p

[0030] In the above Chemical Formula 4, L2 is a ligand selected from the group consisting of cyclopentadienyl and C1-C12 alkyl-substituted cyclopentadienyl, M is a metal selected from the group consisting of titanium, hafnium, and zirconium, and R 7 and R 8 are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and p is 1 or 2.

[0031] [Chemical formula 5] (R9 N) q M(NR 10 R 11 ) 4-q

[0032] In the formula 5, M is a metal selected from the group consisting of vanadium, niobium, tantalum, molybdenum, and tungsten; R 9 , R 10 and R 11 are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and q is 1 or 2.

[0033] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 2 is specifically tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium ((MeCp)Hf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)hafnium ((EtCp)Hf( NMe2)3), (n-propylcyclopentadienyl)tris(dimethylamino)hafnium ((n-PrCp)Hf(NMe2)3), cyclopentadienyltris(methylethylamino)hafnium (CpHf(NMeEt)3), methylcyclopentadienyltris(methylethylamino)hafnium ((MeCp)Hf(NMeEt)3), ethylcyclopentadienyltris(methylethylamino)hafnium ((EtCp)Hf(NMeEt)3), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt2)3), Methylcyclopentadienyl tris(diethylamino)hafnium ((MeCp)Hf(NEt2)3), ethylcyclopentadienyl tris(diethylamino)hafnium ((EtCp)Hf(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp2Hf(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NMe2)2), bis(cyclopentadienyl)bis(dimethylamino)hafnium cyclopentadienyl)bis(methylethylamino)hafnium (Cp2Hf(NMeEt)2), bis(methylcyclopentadienyl)bis(methylethylamino)hafnium ((MeCp)2Hf(NMeEt)2), bis(ethylcyclopentadienyl)bis(methylethylamino)hafnium ((EtCp)2Hf(NMeEt)2), bis(cyclopentadienyl)bis(diethylamino)hafnium (Cp2Hf(NEt2)2), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp)2Hf(NEt2)3),It can be, but is not limited to, bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp)Hf(NEt)) or (n-propylcyclopentadienyl)tris(dimethylamino)zirconium ((n-PrCp)Zr(NMe)).

[0034] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 3 may be, but is not limited to, trimethylaluminum, triethylaluminum, dimethylaluminum isopropoxide, or diethylaluminum isopropoxide.

[0035] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 4 may be, but is not limited to, CpHfMe(OMe)2, CpZrMe(OMe)2, (MeCp)HfMe(OMe)2, (MeCp)ZrMe(OMe)2, (EtCp)HfMe(OMe)2, or (EtCp)ZrMe(OMe).

[0036] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 5 is tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), tert-butyliminotri(ethylmethylamino)tantalum (TBTEMT), ethyliminotri(diethylamino)tantalum (EITDET), ethyliminotri(dimethylamino)tantalum (EITDMT), ethyliminotri(ethylmethylamino)tantalum (EITEMT), It may be, but is not limited to, tert-amyliminotri(dimethylamino)tantalum (TAIMAT), tert-amyliminotri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amyliminotri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, or bis(tert-butylimino)bis(ethylmethylamino)tungsten.

[0037] In a preferred embodiment of the present invention, the precursor for thin film deposition may include a compound represented by the following Formula 2-1.

[0038] [ka]

[0039] In the above chemical formula 2-1, R 3 and R 4 are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group.

[0040] In a preferred embodiment of the present invention, the reactant may include one or more selected from deionized water and hydrogen peroxide (H2O2).

[0041] In a preferred embodiment of the present invention, the area-selective atomic layer deposition process may be performed about 2 to about 100 times.

[0042] In a preferred embodiment of the present invention, the area-selective atomic layer deposition method may form a thin film on the surface of the first substrate to a thickness of about 0.3 Å to about 0.8 Å per cycle, and the thin film may preferably be a hafnium oxide (HfO2) thin film.

[0043] In a preferred embodiment of the present invention, the area-selective atomic layer deposition method may form a thin film on the surface of the second substrate to a thickness of about 0.8 Å to about 1.5 Å per cycle, and the thin film may preferably be a hafnium oxide (HfO2) thin film.

[0044] In a preferred embodiment of the present invention, the area-selective atomic layer deposition method may form a thin film on the surface of the third substrate to a thickness of about 1.5 Å to about 2.5 Å per cycle, and the thin film may preferably be a hafnium oxide (HfO2) thin film.

[0045] Meanwhile, the substrate on which a thin film is selectively formed according to the present invention may include a substrate in which a first substrate containing a metal, a second substrate containing silicon dioxide (SiO2), and a third substrate containing a nitride are arranged in parallel and integrated, and a thin film formed on the surface of the substrate. The metal of the first substrate may be selected from the group consisting of copper (Cu), cobalt (Co), ruthenium (Ru), molybdenum (Mo), and tungsten (W), preferably copper (Cu). The nitride of the third substrate according to the present invention may be selected from the group consisting of titanium nitride, molybdenum nitride, tungsten nitride, and silicon nitride, preferably titanium nitride. The thin film formed on the surface of the substrate may be a thin film selected from the group consisting of metals, metal oxides, and silicon dielectric materials, preferably a hafnium oxide (HfO2) thin film.

[0046] In a preferred embodiment of the present invention, alkylsulfanyl may be adsorbed on the surface of the first substrate.

[0047] In a preferred embodiment of the present invention, the alkylsulfanyl may be ethylsulfanyl.

[0048] In a preferred embodiment of the present invention, alkyl may be adsorbed on the surface of the second substrate.

[0049] In a preferred embodiment of the present invention, the alkyl may be ethyl.

[0050] In a preferred embodiment of the present invention, the substrates on which thin films are selectively formed of the present invention may have different thicknesses of the thin film formed on the surface of the first substrate, the thin film formed on the surface of the second substrate, and the thin film formed on the surface of the third substrate.

[0051] In a preferred embodiment of the present invention, the substrate on which the thin film of the present invention is selectively formed can satisfy the following condition (1).

[0052] (1) A <B<C

[0053] In the above condition (1), A represents the thickness of the thin film formed on the surface of the first substrate, B represents the thickness of the thin film formed on the surface of the second substrate, and C represents the thickness of the thin film formed on the surface of the third substrate. [Effects of the Invention]

[0054] The selective deposition method of a thin film using area-selective atomic layer deposition of the present invention can form thin films with different thicknesses on the surfaces of three or more substrates, for example, a substrate containing a metal, a substrate containing silicon dioxide (SiO2), and a substrate containing a nitride. [Brief explanation of the drawings]

[0055] [Figure 1] 1 is a schematic diagram illustrating that when a substrate is exposed to an organic thiol small molecule inhibitor in the second step of a method for selectively depositing a thin film using area-selective atomic layer deposition, the dissociated organic thiol small molecule inhibitor is adsorbed onto the surface of the substrate. [Figure 2] FIG. 1 is a schematic diagram illustrating that hafnium oxide (HfO2) thin films are formed with different thicknesses on the surface of a substrate by area-selective atomic layer deposition in the third step of a method for selectively depositing a thin film using area-selective atomic layer deposition. [Figure 3] 1 is a graph showing the water contact angle measured for a copper (Cu) substrate, a silicon dioxide (SiO) substrate, and a titanium nitride (TiN) substrate exposed to an organic thiol small molecule inhibitor in Preparatory Examples 1 to 3, as a function of exposure time of the organic thiol small molecule inhibitor (DES Exposure Time). [Figure 4]1 is a graph showing S-2p XPS spectra obtained by X-ray photoelectron spectroscopy (XPS) analysis of copper (Cu) substrates, silicon dioxide (SiO2) substrates, and titanium nitride (TiN) substrates exposed to organic thiol small molecule inhibitors in Preparative Examples 1 to 3, with the internal chamber temperature maintained at 400°C. [Figure 5] 1 is a graph showing S-2p XPS spectra obtained by X-ray photoelectron spectroscopy (XPS) analysis of a copper (Cu) substrate exposed to an organic thiol small molecule inhibitor while maintaining the internal chamber temperature at 200°C and 300°C in Preparation Example 1. [Figure 6] 1 is a graph showing Fourier transform infrared spectroscopy (FT-IR) analysis results for a silicon dioxide (SiO2) substrate (=DES / SiO2) exposed to an organic thiol small molecule inhibitor for 30 seconds while the temperature inside the chamber was maintained at 400°C in Preparation Example 2, and a silicon dioxide (SiO2) substrate (=bare SiO2) not exposed to the organic thiol small molecule inhibitor. [Figure 7] Schematic diagram illustrating the adsorption mechanism of organothiol small molecule inhibitors (DESs) on the surface of silicon dioxide (SiO2) substrates. [Figure 8] 1 is a graph showing the homogeneous selectivity measured as a function of the number of region-selective atomic layer deposition cycles between a copper (Cu) substrate in Comparative Example 1 and a copper (Cu) substrate in Example 1, between a silicon dioxide (SiO) substrate in Comparative Example 2 and a silicon dioxide (SiO) substrate in Example 2, and between a titanium nitride (TiN) substrate in Comparative Example 3 and a titanium nitride (TiN) substrate in Example 3. [Figure 9]1 is a graph showing the heterogeneous selectivity measured as a function of the number of region-selective atomic layer deposition cycles between the copper (Cu) substrate in Example 1 and the silicon dioxide (SiO) substrate in Example 2, between the silicon dioxide (SiO) substrate in Example 2 and the titanium nitride (TiN) substrate in Example 3, and between the titanium nitride (TiN) substrate in Example 3 and the copper (Cu) substrate in Example 1. [Figure 10] 1 is a graph showing the thickness of a hafnium oxide (HfO2) thin film formed on a copper (Cu) substrate in Example 1, the thickness of a hafnium oxide (HfO2) thin film formed on a silicon dioxide (SiO2) substrate in Example 2, and the thickness of a hafnium oxide (HfO2) thin film formed on a titanium nitride (TiN) substrate in Example 3, measured according to the number of cycles of area-selective atomic layer deposition. [Figure 11] 1 is a graph showing the results of analyzing a titanium nitride (TiN) substrate having a silicon dioxide (SiO) pattern formed thereon according to Preparation Example 1, a titanium nitride (TiN) substrate having a silicon dioxide (SiO) pattern formed thereon according to Comparative Preparation Example 1, a titanium nitride (TiN) substrate having a copper (Cu) pattern formed thereon according to Preparation Example 2, and a titanium nitride (TiN) substrate having a copper (Cu) pattern formed thereon according to Comparative Preparation Example 2 using a field-emission scanning electron microscopy (FE-SEM). [Figure 12] 1 is a graph showing an Auger electron spectroscopy (AES) analysis of a titanium nitride (TiN) substrate having a silicon dioxide (SiO2)-copper (Cu) pattern formed thereon in Preparation Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0056] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The present invention will now be described in detail with reference to the accompanying drawings, so that those skilled in the art can easily understand the present invention. The present invention may be embodied in various different forms and is not limited to the embodiments described herein. The same reference numerals will be used throughout the specification to refer to the same or similar elements.

[0057] As used herein, the term "substantially free" is defined as less than 0.001 weight percent (wt%), including 0.000 weight percent (wt%). Also, the term "free" means 0.000 wt%. As used herein, the term "about" is intended to refer to ±5% of the defined number.

[0058] The method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention includes first to third steps.

[0059] In the first step of the method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention, a first substrate, a second substrate, and a third substrate are arranged in parallel to prepare an integrated substrate. The first substrate, the second substrate, and the third substrate may each be made of a different material. The first substrate may comprise a metal, preferably a metal selected from the group consisting of copper (Cu), cobalt (Co), ruthenium (Ru), molybdenum (Mo), and tungsten (W), and more preferably copper (Cu). The second substrate may comprise silicon dioxide (SiO2). The third substrate may comprise a nitride, preferably a nitride selected from the group consisting of titanium nitride, molybdenum nitride, tungsten nitride, and silicon nitride, and more preferably titanium nitride (TiN).

[0060] Next, in the second step of the method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention, the substrate prepared in the first step can be exposed to an organic thiol small molecule inhibitor.

[0061] In this case, the organic thiol small molecule inhibitor may include a compound represented by the following Chemical Formula 1:

[0062] [ka]

[0063] In the above formula 1, R 1 and R 2 are each independently a C1 to C12 linear alkyl group, a C3 to C12 branched alkyl group, or a C6 to C12 aryl group, preferably a C1 to C12 linear alkyl group, and more preferably a C1 to C3 linear alkyl group.

[0064] The organic thiol low-molecular-weight inhibitor may have a weight-average molecular weight of about 300 or less, preferably about 30 to about 150, and more preferably about 60 to about 95.

[0065] Specifically, referring to FIG. 1, the second step of the method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention may include steps 2-1 to 2-3.

[0066] First, in step 2-1 of the selective deposition method of a thin film using area-selective atomic layer deposition of the present invention, the substrate prepared in step 1 is dried, then placed in a chamber having an internal temperature of about 300°C to about 500°C, preferably about 350°C to about 450°C, and a vacuum base pressure, and maintained for about 1 minute to about 20 minutes, preferably about 5 minutes to about 15 minutes. If the internal temperature is less than about 300°C, there may be problems with adsorption of the organic thiol small molecule inhibitor, and if it exceeds about 500°C, there may be problems with desorption and decomposition of the organic thiol small molecule inhibitor.

[0067] Next, in step 2-2 of the selective deposition method of a thin film using area-selective atomic layer deposition of the present invention, the chamber is purged, and the internal temperature of the chamber is maintained at about 200°C to about 500°C, preferably about 350°C to about 450°C, and more preferably about 390°C to about 410°C. An organic thiol small molecule inhibitor is then introduced into the chamber, and the substrate is exposed to the organic thiol small molecule inhibitor for about 1 second to about 100 seconds, preferably about 30 seconds to about 90 seconds, and more preferably about 30 seconds to about 60 seconds. If the internal temperature of the chamber is less than about 200°C, inefficient adsorption of the organic thiol small molecule inhibitor may occur, while if it exceeds about 500°C, desorption and decomposition of the organic thiol small molecule inhibitor may occur.

[0068] Finally, in step 2-3 of the selective deposition method for a thin film using area-selective atomic layer deposition, the substrate exposed to the organic thiol small molecule inhibitor in step 2-2 can be cooled to a temperature of about 15°C to about 35°C, preferably about 20°C to about 30°C.

[0069] Meanwhile, the surface of the first substrate exposed to the organic thiol small molecule inhibitor in the second step of the selective deposition method of a thin film using area-selective atomic layer deposition of the present invention may have a water contact angle of about 90° to about 100°.

[0070] In addition, the surface of the second substrate exposed to the organic thiol small molecule inhibitor in the second step of the selective deposition method for a thin film using area-selective atomic layer deposition of the present invention may have a water contact angle of about 70° to about 80°.

[0071] In addition, in step 2-2 of the selective deposition method of a thin film using area-selective atomic layer deposition of the present invention, the organic thiol small molecule inhibitor introduced into the chamber is thermally dissociated into an alkylsulfanyl and an alkyl, and the alkylsulfanyl is adsorbed on the surface of the first substrate, and the alkyl is adsorbed on the surface of the second substrate. Specifically, the alkylsulfanyl may be ethylsulfanyl, and the alkyl may be ethyl.

[0072] Finally, in the third step of the method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention, area-selective atomic layer deposition (AS-ALD) is used to form a thin film on the surface of the substrate exposed to the organic thiol small molecule inhibitor in the second step.

[0073] In this case, the thickness of the thin film formed on the surface of the first substrate, the thickness of the thin film formed on the surface of the second substrate, and the thickness of the thin film formed on the surface of the third substrate may be different, and preferably satisfy the following condition (1):

[0074] (1) A <B<C

[0075] In the above condition (1), A represents the thickness of the thin film formed on the surface of the first substrate, B represents the thickness of the thin film formed on the surface of the second substrate, and C represents the thickness of the thin film formed on the surface of the third substrate.

[0076] Specifically, referring to FIG. 2, the third step of the method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention may include steps 3-1 and 3-2.

[0077] First, in step 3-1 of the selective deposition method of a thin film using area-selective atomic layer deposition of the present invention, the substrate exposed to the organic thiol small molecule inhibitor in step 2 is placed in a chamber and heated to about 200°C to about 350°C, preferably about 250°C to about 300°C. If the temperature of the substrate exposed to the organic thiol small molecule inhibitor is less than about 200°C, inefficient adsorption of the organic thiol small molecule inhibitor may occur, and if the temperature exceeds about 350°C, decomposition of the organic thiol small molecule inhibitor may occur.

[0078] Next, in step 3-2 of the method for selectively depositing a thin film using area-selective atomic layer deposition of the present invention, a precursor for thin film deposition is introduced into the chamber, exposed for about 1 second to about 10 seconds, preferably about 2 seconds to about 6 seconds, and then purged for about 50 seconds to about 70 seconds, preferably about 55 seconds to about 65 seconds. The area-selective atomic layer deposition can be performed in the following cycles: introducing a precursor for thin film deposition into the chamber, exposing it for about 1 second to about 5 seconds, preferably about 1 second to about 3 seconds, and then purging it for about 50 seconds to about 70 seconds, preferably about 55 seconds to about 65 seconds.

[0079] The precursor for thin film deposition may include at least one compound selected from the group consisting of a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, a compound represented by the following Chemical Formula 4, and a compound represented by the following Chemical Formula 5:

[0080] [Chemical formula 2] (L1) n M(NR 3 R 4 ) 4-n

[0081] In the above formula 2, L1 is a ligand selected from the group consisting of cyclopentadienyl and C1-C12 alkyl-substituted cyclopentadienyl, M is a metal selected from the group consisting of titanium, hafnium, and zirconium, and R 3 and R 4are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group; and n is 0, 1, or 2.

[0082] [Chemical formula 3] R 5 m M(OR 6 ) 3-m

[0083] In the formula 3, M is a metal selected from the group consisting of aluminum, hafnium, and zirconium; R 5 and R 6 are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and m is 1 to 3.

[0084] [Chemical formula 4] (L2) p MR 7 (OR 8 ) 3-p

[0085] In the above Chemical Formula 4, L2 is a ligand selected from the group consisting of cyclopentadienyl and C1-C12 alkyl-substituted cyclopentadienyl, M is a metal selected from the group consisting of titanium, hafnium, and zirconium, and R 7 and R 8 are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and p is 1 or 2.

[0086] [Chemical formula 5] (R 9 N) q M(NR 10 R 11 ) 4-q

[0087] In the formula 5, M is a metal selected from the group consisting of vanadium, niobium, tantalum, molybdenum, and tungsten; R 9 , R 10 and R 11are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and q is 1 or 2.

[0088] The compounds represented by Chemical Formula 2 are specifically tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe2)3), methylcyclopentadienyltris(dimethylamino)hafnium ((MeCp)Hf(NMe2)3), ethylcyclopentadienyltris(dimethylamino)hafnium ((EtCp)Hf(NMe2)3), (n-pro Pyrcyclopentadienyltris(dimethylamino)hafnium ((n-PrCp)Hf(NMe2)3), cyclopentadienyltris(methylethylamino)hafnium (CpHf(NMeEt)3), methylcyclopentadienyltris(methylethylamino)hafnium ((MeCp)Hf(NMeEt)3), ethylcyclopentadienyltris(methylethylamino)hafnium ((EtCp)Hf(NMeEt)3), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt2)3), methylcyclopentadienyl Dienyltris(diethylamino)hafnium ((MeCp)Hf(NEt2)3), ethylcyclopentadienyltris(diethylamino)hafnium ((EtCp)Hf(NEt2)3), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp2Hf(NMe2)2), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp)2Hf(NMe2)2), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp)2Hf(NMe2)2), bis(cyclopentadienyl) bis(methylethylamino)hafnium (Cp2Hf(NMeEt)2), bis(methylcyclopentadienyl)bis(methylethylamino)hafnium ((MeCp)2Hf(NMeEt)2), bis(ethylcyclopentadienyl)bis(methylethylamino)hafnium ((EtCp)2Hf(NMeEt)2), bis(cyclopentadienyl)bis(diethylamino)hafnium (Cp2Hf(NEt2)2), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp)2Hf(NEt2)3),It can be, but is not limited to, bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp)Hf(NEt)) or (n-propylcyclopentadienyl)tris(dimethylamino)zirconium ((n-PrCp)Zr(NMe)).

[0089] In addition, the compound represented by Chemical Formula 3 may be, but is not limited to, trimethylaluminum, triethylaluminum, dimethylaluminum isopropoxide, or diethylaluminum isopropoxide.

[0090] In addition, the compound represented by Chemical Formula 4 may be, but is not limited to, CpHfMe(OMe)2, CpZrMe(OMe)2, (MeCp)HfMe(OMe)2, (MeCp)ZrMe(OMe)2, (EtCp)HfMe(OMe)2, or (EtCp)ZrMe(OMe).

[0091] In addition, the compound represented by Chemical Formula 5 may be tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), tert-butyliminotri(ethylmethylamino)tantalum (TBTEMT), ethyliminotri(diethylamino)tantalum (EITDET), ethyliminotri(dimethylamino)tantalum (EITDMT), ethyliminotri(ethylmethylamino)tantalum (EITEMT), tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), tert-butyliminotri(ethylmethylamino)tantalum (TBTEMT), tert-butyliminotri(diethylamino)tantalum (EITDET), tert-butyliminotri(dimethylamino)tantalum (EITDMT), tert-butyliminotri(ethylmethylamino)tantalum (EITEMT), tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), tert-butyliminotri(ethylmethylamino)tantalum (TBTD ... The tungsten compound may be, but is not limited to, tungsten, tert-amyliminotri(dimethylamino)tantalum (TAIMAT), tert-amyliminotri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amyliminotri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, or bis(tert-butylimino)bis(ethylmethylamino)tungsten.

[0092] Most preferably, the precursor for thin film deposition may include a compound represented by the following Formula 2-1:

[0093] [ka]

[0094] In the above chemical formula 2-1, R 3 and R 4 are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, preferably a C1 to C12 linear alkyl group, and more preferably a C1 to C3 linear alkyl group.

[0095] The reactant may include at least one selected from deionized water and hydrogen peroxide (H2O2), and preferably deionized water.

[0096] Meanwhile, the area-selective atomic layer deposition may be performed about 2 to about 100 times, preferably about 10 to about 25 times, and more preferably about 10 to about 15 times.

[0097] In addition, the area-selective atomic layer deposition method can form a thin film on the surface of the first substrate with a thickness of about 0.3 Å to about 0.8 Å, preferably about 0.4 Å to about 0.6 Å per period.

[0098] In addition, the area-selective atomic layer deposition method can form a thin film on the surface of the second substrate with a thickness of about 0.8 Å to about 1.5 Å, preferably about 1.1 Å to about 1.3 Å per period.

[0099] In addition, the area-selective atomic layer deposition method can form a thin film on the surface of the third substrate with a thickness of about 1.5 Å to about 2.5 Å, preferably about 1.8 Å to about 2.2 Å per period.

[0100] Meanwhile, the thin film formed on the surface of the substrate may be a thin film selected from the group consisting of metals, metal oxides, and silicon dielectric materials, and preferably a hafnium oxide (HfO2) thin film.

[0101] Furthermore, the substrate on which a thin film of the present invention is selectively formed may include a substrate in which a first substrate containing a metal, a second substrate containing silicon dioxide (SiO2), and a third substrate containing a nitride are arranged in parallel and integrated, and a thin film formed on the surface of the substrate. In this case, alkylsulfanyl, preferably ethylsulfanyl, may be adsorbed on the surface of the first substrate. Also, alkyl, preferably ethyl, may be adsorbed on the surface of the second substrate.

[0102] On the other hand, the metal of the first substrate may be selected from the group consisting of copper (Cu), cobalt (Co), ruthenium (Ru), molybdenum (Mo) and tungsten (W), and is preferably copper (Cu).

[0103] Furthermore, the nitride of the third substrate according to the present invention may be selected from the group consisting of titanium nitride, molybdenum nitride, tungsten nitride and silicon nitride, and preferably titanium nitride.

[0104] The thin film formed on the surface of the substrate is a thin film selected from the group consisting of metals, metal oxides, and silicon dielectric materials, and is preferably a hafnium oxide (HfO2) thin film.

[0105] Furthermore, the substrate on which the thin film of the present invention is selectively formed may have different thicknesses of the thin film formed on the surface of the first substrate, the second substrate, and the third substrate, and preferably satisfies the following condition (1):

[0106] (1) A <B<C

[0107] In the above condition (1), A represents the thickness of the thin film formed on the surface of the first substrate, B represents the thickness of the thin film formed on the surface of the second substrate, and C represents the thickness of the thin film formed on the surface of the third substrate.

[0108] While the present invention has been described above with reference to exemplary embodiments, these are merely illustrative and do not limit the scope of the present invention. Those skilled in the art will recognize that various modifications and applications not exemplified above are possible without departing from the essential characteristics of the present invention. For example, the components specifically illustrated in the exemplary embodiments of the present invention may be modified and implemented. Differences related to such modifications and applications should be construed as being included within the scope of the present invention as defined in the appended claims. [Example]

[0109] Preparation Example 1: Exposing a copper (Cu) substrate to an organic thiol small molecule inhibitor

[0110] (1) A copper (Cu) substrate was ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, in that order, for 10 minutes.

[0111] (2) The cleaned copper (Cu) substrate was dried with nitrogen gas (N2 gas) and then placed in a chamber with an internal temperature of 400°C and a vacuum base pressure, and maintained for 10 minutes.

[0112] (3) A stainless steel canister was prepared, maintaining an internal temperature of 25° C., and storing an organic thiol small molecule inhibitor. The organic thiol small molecule inhibitor was a compound represented by the following Chemical Formula 1:

[0113] [ka]

[0114] In the above formula 1, R 1 and R 2 is an ethyl group.

[0115] (4) The copper (Cu) substrate was connected to the stainless steel canister so that the substrate could be exposed to the compound represented by Formula 1.

[0116] (5) The chamber was purged with nitrogen gas (N2 gas), and the temperature inside the chamber was maintained at 200°C, 300°C, and 400°C, respectively. The copper (Cu) substrate was exposed to the compound represented by Formula 1 for 0, 15, 30, 60, and 90 seconds, respectively.

[0117] (6) The copper (Cu) substrate exposed to the compound represented by Chemical Formula 1 was cooled at a temperature of 25°C.

[0118] Preparation Example 2: Exposing a silicon dioxide (SiO2) substrate to an organic thiol small molecule inhibitor

[0119] (1) A silicon dioxide (SiO2) substrate was ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, in that order, for 10 minutes.

[0120] (2) The cleaned silicon dioxide (SiO2) substrate was dried with nitrogen gas (N2 gas) and then placed in a chamber with an internal temperature of 400°C and a vacuum base pressure, and maintained for 10 minutes.

[0121] (3) A stainless steel canister was prepared, maintaining an internal temperature of 25° C., and storing an organic thiol small molecule inhibitor. The organic thiol small molecule inhibitor was a compound represented by the following Chemical Formula 1:

[0122] [ka]

[0123] In the above formula 1, R 1 and R 2 is an ethyl group.

[0124] (4) The silicon dioxide (SiO2) substrate was connected to the stainless steel canister so that the substrate could be exposed to the compound represented by Chemical Formula 1.

[0125] (5) The chamber was purged with nitrogen gas (N2 gas), and the temperature inside the chamber was maintained at 200°C, 300°C, and 400°C, respectively. The silicon dioxide (SiO2) substrate was exposed to the compound represented by Formula 1 for 0, 15, 30, 60, and 90 seconds, respectively.

[0126] (6) The silicon dioxide (SiO2) substrate exposed to the compound represented by Chemical Formula 1 was cooled at a temperature of 25°C.

[0127] Preparation Example 3: Exposing a titanium nitride (TiN) substrate to an organic thiol small molecule inhibitor

[0128] (1) A titanium nitride (TiN) substrate was ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, in that order, for 10 minutes.

[0129] (2) The cleaned titanium nitride (TiN) substrate was dried with nitrogen gas (N2 gas) and then placed in a chamber having an internal temperature of 400°C and a vacuum base pressure, and maintained for 10 minutes.

[0130] (3) A stainless steel canister was prepared, maintaining an internal temperature of 25° C., and storing an organic thiol small molecule inhibitor. The organic thiol small molecule inhibitor was a compound represented by the following Chemical Formula 1:

[0131] [ka]

[0132] In the above formula 1, R 1 and R 2 is an ethyl group.

[0133] (4) The titanium nitride (TiN) substrate was connected to the stainless steel canister so that the substrate could be exposed to the compound represented by Formula 1.

[0134] (5) The chamber was purged with nitrogen gas (N2 gas), and the internal temperature of the chamber was maintained at 200°C, 300°C, and 400°C, respectively. The titanium nitride (TiN) substrate was exposed to the compound represented by Formula 1 for 0, 15, 30, 60, and 90 seconds, respectively.

[0135] (6) The titanium nitride (TiN) substrate exposed to the compound represented by Chemical Formula 1 was cooled at a temperature of 25°C.

[0136] Experimental Example 1: Water contact angle measurement

[0137] The water contact angles were measured for copper (Cu), silicon dioxide (SiO2), and titanium nitride (TiN) substrates exposed to the organic thiol small molecule inhibitors in Preparation Examples 1 to 3, and the results are shown in Figure 3. Specifically, the left graph in Figure 3 shows the Mohr contact angle of the copper (Cu) substrate in Preparation Example 1 as a function of the exposure time to the organic thiol small molecule inhibitor (DES Exposure Time). The middle graph in Figure 3 shows the Mohr contact angle of the silicon dioxide (SiO2) substrate in Preparation Example 2 as a function of the exposure time to the organic thiol small molecule inhibitor (DES Exposure Time). The right graph in Figure 3 shows the Mohr contact angle of the titanium nitride (TiN) substrate in Preparation Example 3 as a function of the exposure time to the organic thiol small molecule inhibitor (DES Exposure Time). The water contact angles were measured using a contact angle measuring instrument (SDL200TEZD, Femtobiomed) using deionized water as the measurement source and a droplet size of 2 μl.

[0138] As can be seen in the graph on the left side of Figure 3, the water contact angle of the copper (Cu) substrate surface gradually increased from 55°. Furthermore, with the chamber internal temperature maintained at 200°C, the copper (Cu) substrate exposed to the organic thiol small molecule inhibitor saturated at approximately 75° as the exposure time increased. Furthermore, with the chamber internal temperature maintained at 300°C, the copper (Cu) substrate exposed to the organic thiol small molecule inhibitor increased from 55° to approximately 68° after 15 seconds of exposure and saturated at approximately 80° after 60 seconds. Furthermore, with the chamber internal temperature maintained at 400°C, the copper (Cu) substrate exposed to the organic thiol small molecule inhibitor increased from 55° to approximately 95° after 15 seconds of exposure and saturated at approximately 98° after 30 seconds. From these results, it was confirmed that the gradual increase in the water contact angle of the copper (Cu) substrate at chamber internal temperatures of 200°C and 300°C is due to the limited adsorption of the organic thiol small molecule inhibitor at low temperatures.

[0139] As can be seen in the middle graph of Figure 3, the water contact angle of the silicon dioxide (SiO2) substrate exposed to the organic thiol small molecule inhibitor with the chamber internal temperature maintained at 200°C increased from 44° to approximately 55° after 30 seconds of exposure and saturated at approximately 62° after 60 seconds. Furthermore, the water contact angle of the silicon dioxide (SiO2) substrate exposed to the organic thiol small molecule inhibitor with the chamber internal temperature maintained at 300°C increased from 44° to approximately 65° after 30 seconds of exposure and saturated. Furthermore, the water contact angle of the silicon dioxide (SiO2) substrate exposed to the organic thiol small molecule inhibitor with the chamber internal temperature maintained at 400°C increased from 44° to approximately 76° after 15 seconds of exposure and saturated at approximately 80° after 30 seconds.

[0140] As can be seen in the graph on the right side of Figure 3, the titanium nitride (TiN) substrate exposed to the organic thiol small molecule inhibitor while the internal chamber temperature was maintained at 300°C and 400°C did not show a significant increase in water contact angle even when the exposure time to the organic thiol small molecule inhibitor was increased. This result confirmed that the organic thiol small molecule inhibitor did not change the surface properties of the titanium nitride (TiN) substrate.

[0141] Experimental example 2: XPS analysis

[0142] In Preparatory Examples 1 to 3, the temperature inside the chamber was maintained at 400°C, and the copper (Cu) substrate (30-second exposure), silicon dioxide (SiO2) substrate (30-second exposure), and titanium nitride (TiN) substrate (30-second exposure) were exposed to the organic thiol small molecule inhibitor. X-ray photoelectron spectroscopy (XPS) analysis was performed on each of these substrates, and the results are shown in Figure 4. Specifically, the S-2p peak was examined to confirm the presence of organic thiol small molecule inhibitors on copper (Cu), silicon dioxide (SiO2), and titanium nitride (TiN) substrates. The left graph in Figure 4 shows the S-2p XPS spectrum of a copper (Cu) substrate exposed to an organic thiol small molecule inhibitor while the internal chamber temperature was maintained at 400°C in Preparation Example 1. The middle graph in Figure 4 shows the S-2p XPS spectrum of a silicon dioxide (SiO2) substrate exposed to an organic thiol small molecule inhibitor while the internal chamber temperature was maintained at 400°C in Preparation Example 2. The right graph in Figure 4 shows the S-2p XPS spectrum of a titanium nitride (TiN) substrate exposed to an organic thiol small molecule inhibitor while the internal chamber temperature was maintained at 400°C in Preparation Example 3. XPS analysis was performed using an XPS system (PHI-5000 Versa Probe II, ULVAC, Physical Electronics) using monochromatic Al Kα radiation as a source.

[0143] As can be seen in the graph on the left side of Figure 4, the S-2p XPS spectrum of the copper (Cu) substrate exposed to the organic thiol small molecule inhibitor while maintaining the internal chamber temperature at 400°C in Preparation Example 1 clearly shows an S-2p peak. Specifically, a core electron peak was observed in the S-2p region. The S-2p peak was in the range of 159 to 164 eV. When the S-2p peak was deconvoluted, two chemical bonds of S-2p were confirmed, and here, an S2p peak at 161.0 eV was observed. 3 / 2 and S2p at 162.5 eV 1 / 2The S-2p peak indicates the adsorption of the thiol group of the organic thiol small molecule inhibitor onto the surface of the copper (Cu) substrate. At high temperatures, the organic thiol small molecule inhibitor undergoes thermal dissociation to form ethylsulfanyl. Due to the alkaline nature of the copper (Cu) substrate, only ethylsulfanyl, which has acidic properties, can be adsorbed onto the copper (Cu) substrate. Consequently, in Preparation Example 1, when the chamber internal temperature was maintained at 400°C, ethylsulfanyl was adsorbed and bonded to the copper (Cu) substrate surface exposed to the organic thiol small molecule inhibitor. Furthermore, the adsorbed ethylsulfanyl rendered the copper (Cu) substrate surface hydrophobic, thereby passivating the copper (Cu) substrate surface.

[0144] In addition, as can be seen in the left graph of Figure 4, the XPS spectrum of the copper (Cu) substrate exposed to the organic thiol small molecule inhibitor while maintaining the internal chamber temperature at 400°C in Preparation Example 1 confirmed the absence of oxidized sulfur such as sulfonate, which has a binding energy higher than 166 eV.

[0145] As can be seen in the middle graph of Figure 4, in Preparation Example 2, the S-2p characteristic peak was not observed in the S-2p XPS spectrum of the silicon dioxide (SiO2) substrate exposed to the organic thiol small molecule inhibitor while the internal temperature of the chamber was maintained at 400°C, which indicates that no thiol groups were present on the surface of the silicon dioxide (SiO2) substrate.

[0146] Furthermore, as can be seen in the graph on the right side of Figure 4, no S-2p characteristic peak was observed in the S-2p XPS spectrum of the titanium nitride (TiN) substrate exposed to the organic thiol small molecule inhibitor while the internal temperature of the chamber was maintained at 400°C in Preparation Example 3, which also indicates that no thiol groups exist on the surface of the titanium nitride (TiN) substrate.

[0147] Additionally, Figure 5 shows the S-2p XPS spectra of copper (Cu) substrates exposed to an organic thiol small molecule inhibitor for 30 seconds while the internal chamber temperatures were maintained at 200°C and 300°C, respectively, in Preparation Example 1.

[0148] As can be seen in Figure 5, in Preparation Example 1, no S-2p peak was observed in the S-2p XPS spectrum of the copper (Cu) substrate exposed to the organic thiol small molecule inhibitor while the internal chamber temperature was maintained at 200°C and 300°C, respectively.

[0149] Experimental Example 3: FT-IR analysis

[0150] In Preparation Example 2, the temperature inside the chamber was maintained at 400°C, and a silicon dioxide (SiO2) substrate exposed to an organic thiol small molecule inhibitor for 30 seconds (DES / SiO2) and a silicon dioxide (SiO2) substrate not exposed to the organic thiol small molecule inhibitor (bare SiO2) were analyzed by Fourier transform infrared spectroscopy (FT-IR), and the results are shown in Figure 6.

[0151] FT-IR analysis was performed using a Bruker spectrometer (VERTEX 80V, HYPERION 2000) in ATR (attenuative total reflectance) mode at 8000–800 cm -1 The FT-IR absorption spectrum was measured and analyzed at wavenumber.

[0152] As can be seen in Figure 6, the spectrum of the silicon dioxide (SiO2) substrate exposed to the organic thiol small molecule inhibitor while the internal chamber temperature was maintained at 400 °C in Preparation Example 2 shows a peak at 2975 cm2 indicating the presence of CH stretching. -1 A peak is seen at 945 cm, which represents the CH bending vibration. -1 It was confirmed that peaks were visible at . These two peaks were not observed on the silicon dioxide (SiO2) substrate that was not exposed to the organic thiol small molecule inhibitor, indicating the presence of alkyl groups on the surface of the silicon dioxide (SiO2) substrate that was exposed to the organic thiol small molecule inhibitor while the internal chamber temperature was maintained at 400°C in Preparation Example 2. These results confirmed that the organic thiol small molecule inhibitor was thermally dissociated at high temperatures to separate into ethyl groups, and that the separated ethyl groups were adsorbed and bonded to the surface of the silicon dioxide (SiO2) substrate.

[0153] Meanwhile, Figure 7 illustrates the adsorption mechanism of organic thiol small molecule inhibitors (DES) on the surface of a silicon dioxide (SiO2) substrate. When an SiO2 substrate is exposed to an organic thiol small molecule inhibitor while the internal temperature of a high-temperature chamber is maintained at 400°C, the organic thiol small molecule inhibitor (DES) undergoes thermal dissociation and dissociates into ethylsulfanyl (EtS) and ethyl (Et), and the dissociated ethyl (Et) is adsorbed to -OH present on the surface of the silicon dioxide (SiO2) substrate.

[0154] Example 1: Hafnium oxide (HfO2) thin film formation on copper (Cu) substrate exposed to an organic thiol small molecule inhibitor

[0155] Area selective atomic layer deposition (AS-ALD) was used to form a hafnium oxide (HfO2) thin film on a copper (Cu) substrate that had been exposed to an organic thiol small molecule inhibitor for 30 seconds while maintaining the chamber internal temperature at 400°C in Preparation Example 1. The area selective atomic layer deposition used the compound represented by Formula 2-1 below as the thin film deposition precursor and deionized water as the counter reactant.

[0156] [ka]

[0157] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0158] Specifically, a stainless-steel canister storing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister storing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a copper (Cu) substrate, and area-selective atomic layer deposition was performed with the copper (Cu) substrate heated to 275°C. Nitrogen gas (N2 gas) was used at a flow rate of 10 sccm for purging during area-selective atomic layer deposition, and this was controlled by a mass flow controller (MFC).

[0159] Meanwhile, the area-selective atomic layer deposition method was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a copper (Cu) substrate, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a copper (Cu) substrate, exposed for 2 seconds, and then purged for 60 seconds.

[0160] The area-selective atomic layer deposition was performed 2 times, 10 times, 25 times, 50 times, and 100 times, respectively.

[0161] Example 2: Hafnium oxide (HfO2) thin film formation on silicon dioxide (SiO2) substrates exposed to an organic thiol small molecule inhibitor

[0162] Area-selective atomic layer deposition (AS-ALD) was used to form a hafnium oxide (HfO) thin film on a silicon dioxide (SiO) substrate that had been exposed to an organic thiol small molecule inhibitor for 30 seconds while maintaining the chamber internal temperature at 400°C in Preparation Example 2. The area-selective atomic layer deposition used the compound represented by Formula 2-1 below as the precursor for thin film deposition, and deionized water as the counter reactant.

[0163] [ka]

[0164] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0165] Specifically, a stainless-steel canister containing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister containing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a silicon dioxide (SiO2) substrate, and area-selective atomic layer deposition was performed with the silicon dioxide (SiO2) substrate heated to 275°C. Nitrogen gas (N2 gas) was used for purging at a flow rate of 10 sccm during area-selective atomic layer deposition, and this was controlled by a mass flow controller (MFC).

[0166] Meanwhile, the area-selective atomic layer deposition method was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a silicon dioxide (SiO2) substrate, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a silicon dioxide (SiO2) substrate, exposed for 2 seconds, and then purged for 60 seconds.

[0167] The area-selective atomic layer deposition was performed 2 times, 10 times, 25 times, 50 times, and 100 times, respectively.

[0168] Example 3: Hafnium oxide (HfO2) thin film formation on titanium nitride (TiN) substrate exposed to an organic thiol small molecule inhibitor

[0169] Area selective atomic layer deposition (AS-ALD) was used to form a hafnium oxide (HfO2) thin film on a titanium nitride (TiN) substrate that had been exposed to an organic thiol small molecule inhibitor for 30 seconds while maintaining the chamber internal temperature at 400°C in Preparation Example 3. The area selective atomic layer deposition used the compound represented by Formula 2-1 below as the thin film deposition precursor and deionized water as the counter reactant.

[0170] [ka]

[0171] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0172] Specifically, a stainless-steel canister storing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister storing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a titanium nitride (TiN) substrate, and area-selective atomic layer deposition was performed with the titanium nitride (TiN) substrate heated to 275°C. Nitrogen gas (N2 gas) was used for purging at a flow rate of 10 sccm during area-selective atomic layer deposition, and this was controlled by a mass flow controller (MFC).

[0173] Meanwhile, the area-selective atomic layer deposition method was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a titanium nitride (TiN) substrate, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a titanium nitride (TiN) substrate, exposed for 2 seconds, and then purged for 60 seconds.

[0174] The area-selective atomic layer deposition was performed 2 times, 10 times, 25 times, 50 times, and 100 times, respectively.

[0175] Comparative Example 1: Hafnium oxide (HfO2) thin film formed on copper (Cu) substrate

[0176] A hafnium oxide (HfO2) thin film was formed on a copper (Cu) substrate using area selective atomic layer deposition (AS-ALD). The compound represented by Formula 2-1 below was used as the precursor for thin film deposition, and deionized water was used as the reactant.

[0177] [ka]

[0178] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0179] Specifically, a stainless-steel canister storing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister storing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a copper (Cu) substrate, and area-selective atomic layer deposition was performed with the copper (Cu) substrate heated to 275°C. Nitrogen gas (N2 gas) was used at a flow rate of 10 sccm for purging during area-selective atomic layer deposition, and this was controlled by a mass flow controller (MFC).

[0180] Meanwhile, the area-selective atomic layer deposition method was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a copper (Cu) substrate, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a copper (Cu) substrate, exposed for 2 seconds, and then purged for 60 seconds.

[0181] The area-selective atomic layer deposition was performed 2 times, 10 times, 25 times, 50 times, and 100 times, respectively.

[0182] Comparative Example 2: Hafnium oxide (HfO2) thin film formation on silicon dioxide (SiO2) substrate

[0183] A hafnium oxide (HfO2) thin film was formed on a silicon dioxide (SiO2) substrate using area selective atomic layer deposition (AS-ALD). The compound represented by Formula 2-1 below was used as the precursor for thin film deposition, and deionized water was used as the reactant.

[0184] [ka]

[0185] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0186] Specifically, a stainless-steel canister containing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister containing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a silicon dioxide (SiO2) substrate, and area-selective atomic layer deposition was performed with the silicon dioxide (SiO2) substrate heated to 275°C. Nitrogen gas (N2 gas) was used for purging at a flow rate of 10 sccm during area-selective atomic layer deposition, and this was controlled by a mass flow controller (MFC).

[0187] Meanwhile, the area-selective atomic layer deposition method was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a silicon dioxide (SiO2) substrate, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a silicon dioxide (SiO2) substrate, exposed for 2 seconds, and then purged for 60 seconds.

[0188] The area-selective atomic layer deposition was performed 2 times, 10 times, 25 times, 50 times, and 100 times, respectively.

[0189] Comparative Example 3: Hafnium oxide (HfO2) thin film formed on titanium nitride (TiN) substrate

[0190] A hafnium oxide (HfO2) thin film was formed on a titanium nitride (TiN) substrate using area selective atomic layer deposition (AS-ALD). The compound shown in Formula 2-1 below was used as the precursor for thin film deposition, and deionized water was used as the reactant.

[0191] [ka]

[0192] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0193] Specifically, a stainless-steel canister storing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister storing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a titanium nitride (TiN) substrate, and area-selective atomic layer deposition was performed with the titanium nitride (TiN) substrate heated to 275°C. Nitrogen gas (N2) was used for purging at a flow rate of 10 sccm during area-selective atomic layer deposition, and this was controlled by a mass flow controller (MFC).

[0194] Meanwhile, the area-selective atomic layer deposition method was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a titanium nitride (TiN) substrate, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a titanium nitride (TiN) substrate, exposed for 2 seconds, and then purged for 60 seconds.

[0195] The area-selective atomic layer deposition was performed 2 times, 10 times, 25 times, 50 times, and 100 times, respectively.

[0196] Experimental Example 4: Selectivity measurement by number of cycles in area-selective atomic layer deposition

[0197] The selectivity was calculated based on the difference in atomic concentration between the growth area (GS) and the non-growth area (NGS) using the following equation 1:

[0198]

number

[0199] In Equation 1 above,

number

[0200] The homogeneous selectivity as a function of the number of region-selective atomic layer deposition cycles between a copper (Cu) substrate on which a hafnium oxide (HfO2) thin film was formed in Comparative Example 1 and a copper (Cu) substrate on which a hafnium oxide (HfO2) thin film was formed in Example 1 was measured and is shown in Figure 8 (shown as Cu w / & w / o DES).

[0201] As can be seen in Figure 8, the homogeneity selectivity of the surface of the copper (Cu) substrate for forming a hafnium oxide (HfO2) thin film on the substrate was measured as 100% after 2 cycles, 99.8% after 10 cycles, 98% after 25 cycles, 55% after 50 cycles, and 24.8% after 100 cycles.

[0202] In addition, the uniformity selectivity as a function of the number of cycles of the area-selective atomic layer deposition method between a silicon dioxide (SiO2) substrate on which a hafnium oxide (HfO2) thin film is formed in Comparative Example 2 and a silicon dioxide (SiO2) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 2 was measured and is shown in Figure 8 (=SiO2 w / & w / o DES).

[0203] In addition, the uniformity selectivity as a function of the number of region-selective atomic layer deposition cycles between a titanium nitride (TiN) substrate on which a hafnium oxide (HfO2) thin film was formed in Comparative Example 3 and a titanium nitride (TiN) substrate on which a hafnium oxide (HfO2) thin film was formed in Example 3 was measured and is shown in Figure 8 (=TiN w / & w / o DES).

[0204] As can be seen in Figure 8, the homogeneity selectivity of the surface of a silicon dioxide (SiO2) substrate for forming a hafnium oxide (HfO2) thin film on the substrate was measured to be 61% after 2 cycles, 27% after 10 cycles, 19% after 25 cycles, 9% after 50 cycles, and 6% after 100 cycles.

[0205] In addition, it was confirmed that there was no uniform selectivity between the titanium nitride (TiN) substrate on which a hafnium oxide (HfO2) thin film was formed in Comparative Example 3 and the titanium nitride (TiN) substrate on which a hafnium oxide (HfO2) thin film was formed in Example 3.

[0206] From these results, it was confirmed that the surface of a copper (Cu) substrate on which a hafnium oxide (HfO2) thin film is formed and the surface of a silicon dioxide (SiO2) substrate on which a hafnium oxide (HfO2) thin film is formed both show a decrease in uniformity selectivity as the number of area-selective atomic layer deposition cycles increases, and that the surface of a copper (Cu) substrate on which a hafnium oxide (HfO2) thin film is formed has better uniformity selectivity.

[0207] Meanwhile, the heterogeneous selectivity as a function of the number of cycles of area-selective atomic layer deposition between a copper (Cu) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 1 and a silicon dioxide (SiO2) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 2 was measured and shown in Figure 9 (=shown as b / w DES on Cu & SiO2).

[0208] In addition, the heterogeneous selectivity as a function of the number of region-selective atomic layer deposition cycles between a silicon dioxide (SiO) substrate on which a hafnium oxide (HfO) thin film was formed in Example 2 and a titanium nitride (TiN) substrate on which a hafnium oxide (HfO) thin film was formed in Example 3 was measured and shown in Figure 9 (=b / w DES on Cu & TiN).

[0209] In addition, the heterogeneous selectivity between a titanium nitride (TiN) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 3 and a copper (Cu) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 1 was measured as a function of the number of cycles of the area-selective atomic layer deposition method, and the results are shown in Figure 9 (=b / w DES on SiO2 & TiN).

[0210] As can be seen in Figure 9, the heterogeneity selectivity depending on the number of cycles of the area-selective atomic layer deposition method between a copper (Cu) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 1 and a silicon dioxide (SiO2) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 2 was measured to be 100% from 2 cycles to 25 cycles, 52.4% at 50 cycles, and 47.6% at 100 cycles.

[0211] In addition, the heterogeneity selectivity depending on the number of cycles of the area-selective atomic layer deposition method between a silicon dioxide (SiO2) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 2 and a titanium nitride (TiN) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 3 was measured to be 100% for 2 cycles, 99.2% for 10 cycles, 98.1% for 25 cycles, 31.7% for 50 cycles, and 25.2% for 100 cycles.

[0212] In addition, the heterogeneity selectivity depending on the number of cycles of the area-selective atomic layer deposition method between a titanium nitride (TiN) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 3 and a copper (Cu) substrate on which a hafnium oxide (HfO2) thin film is formed in Example 1 was measured to be 68.5% for 2 cycles, 42.1% for 10 cycles, 35.9% for 25 cycles, 25.8% for 50 cycles, and 21.2% for 100 cycles.

[0213] Experimental Example 5: Thickness measurement of hafnium oxide (HfO2) thin film by area-selective atomic layer deposition cycle number

[0214] The thickness of the hafnium oxide (HfO2) thin film formed on a copper (Cu) substrate in Example 1 (expressed as HfO2 / DES / CuO), the thickness of the hafnium oxide (HfO2) thin film formed on a silicon dioxide (SiO2) substrate in Example 2 (expressed as HfO2 / DES / SiO2), and the thickness of the hafnium oxide (HfO2) thin film formed on a titanium nitride (TiN) substrate in Example 3 (expressed as HfO2 / DES / TiN) were measured depending on the number of cycles of the area-selective atomic layer deposition method, and the results are shown in Figure 10.

[0215] As can be seen in Figure 10, it was observed that the formation of a hafnium oxide (HfO2) thin film on a copper (Cu) substrate was delayed up to 25 cycles, and that the formation of a hafnium oxide (HfO2) thin film began after 25 cycles. From these results, it was confirmed that the organic thiol small molecule inhibitor adsorbed on the surface of the copper (Cu) substrate delayed the formation of a hafnium oxide (HfO2) thin film up to 25 cycles, and that this delay effect was lost after 25 cycles.

[0216] On the other hand, silicon dioxide (SiO2) and titanium nitride (TiN) substrates did not exhibit the delayed formation of hafnium oxide (HfO2) thin films that occurs on copper (Cu) substrates, and this delayed formation effect of hafnium oxide (HfO2) thin films was observed most effectively on copper (Cu) substrates, followed by silicon dioxide (SiO2) and titanium nitride (TiN) substrates. In particular, no delayed formation effect of hafnium oxide (HfO2) thin films was observed on titanium nitride (TiN) substrates.

[0217] Specifically, in Example 1, the thickness of the hafnium oxide (HfO2) thin film formed on the copper (Cu) substrate was measured to be 0 nm at 2 cycles, 0 nm at 10 cycles, 0 nm at 25 cycles, 2.95 nm at 50 cycles, and 5.91 nm at 100 cycles.

[0218] Furthermore, in Example 2, the thickness of the hafnium oxide (HfO2) thin film formed on the silicon dioxide (SiO2) substrate was measured to be 0.35 nm for 2 cycles, 1.37 nm for 10 cycles, 2.43 nm for 25 cycles, 5.56 nm for 50 cycles, and 9.90 nm for 100 cycles.

[0219] Furthermore, in Example 3, the thickness of the hafnium oxide (HfO2) thin film formed on the titanium nitride (TiN) substrate was measured to be 2.43 nm for 2 cycles, 4.25 nm for 10 cycles, 5.16 nm for 25 cycles, 9.43 nm for 50 cycles, and 16.66 nm for 100 cycles.

[0220] Manufacturing Example 1: Formation of a hafnium oxide (HfO2) thin film on a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern

[0221] (1) Silicon dioxide (SiO2) patterns were formed on titanium nitride (TiN) substrates using the drop casting method. The SiO2 patterns were formed using a 0.1M solution of silicon dioxide (SiO2) powder dispersed in 50 ml of ethanol, and the remaining solution after the SiO2 pattern formation was evaporated at 22°C.

[0222] (2) A titanium nitride (TiN) substrate on which a silicon dioxide (SiO2) pattern was formed was ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, in that order, for 10 minutes.

[0223] (3) The cleaned titanium nitride (TiN) substrate with the silicon dioxide (SiO2) pattern formed thereon was dried with nitrogen gas (N2 gas), and then placed in a chamber having an internal temperature of 400°C and a vacuum base pressure, and maintained there for 10 minutes.

[0224] (4) A stainless steel canister was prepared, maintaining an internal temperature of 25° C. and storing an organic thiol small molecule inhibitor. The organic thiol small molecule inhibitor used was a compound represented by the following Chemical Formula 1:

[0225] [ka]

[0226] In the above formula 1, R 1 and R 2 is an ethyl group.

[0227] (5) The titanium nitride (TiN) substrate on which the silicon dioxide (SiO2) pattern was formed was connected to the stainless steel canister so that the substrate could be exposed to the compound represented by Chemical Formula 1.

[0228] (6) The chamber was purged with nitrogen gas (N2 gas), and the temperature inside the chamber was maintained at 400°C. The titanium nitride (TiN) substrate on which the silicon dioxide (SiO2) pattern was formed was exposed to the compound represented by Formula 1 for 30 seconds.

[0229] (7) The titanium nitride (TiN) substrate on which the silicon dioxide (SiO2) pattern was formed and exposed to the compound represented by Chemical Formula 1 was cooled at a temperature of 25°C.

[0230] (8) Using area-selective atomic layer deposition (AS-ALD), a hafnium oxide (HfO2) thin film was formed on a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern exposed to an organic thiol small molecule inhibitor. The compound represented by the following formula 2-1 was used as the thin film deposition precursor, and deionized water was used as the counter reactant.

[0231] [ka]

[0232] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0233] Specifically, a stainless-steel canister containing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister containing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern. Area-selective atomic layer deposition was performed with the titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern heated to 275°C. Nitrogen gas (N2 gas) was used for purging at a flow rate of 10 sccm, and the flow rate was controlled by a mass flow controller (MFC).

[0234] Meanwhile, the area-selective atomic layer deposition (ALD) process was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern, exposed for 2 seconds, and then purged for 60 seconds. The ALD process was performed 10 times.

[0235] Manufacturing example 2: Formation of a hafnium oxide (HfO2) thin film on a titanium nitride (TiN) substrate with a copper (Cu) pattern

[0236] (1) A copper (Cu) pattern was formed on a titanium nitride (TiN) substrate using the drop casting method. The copper (Cu) pattern was formed using a 0.1M solution in which copper (Cu) powder was dispersed in 50 ml of ethanol, and the remaining solution after the copper (Cu) pattern formation was evaporated at 22°C.

[0237] (2) The titanium nitride (TiN) substrate on which the copper (Cu) pattern was formed was ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, in that order, for 10 minutes.

[0238] (3) The titanium nitride (TiN) substrate with the cleaned copper (Cu) pattern formed thereon was dried with nitrogen gas (N2 gas), and then placed in a chamber having an internal temperature of 400°C and a vacuum base pressure, and maintained for 10 minutes.

[0239] (4) A stainless steel canister was prepared, maintaining an internal temperature of 25° C. and storing an organic thiol small molecule inhibitor. The organic thiol small molecule inhibitor used was a compound represented by the following Chemical Formula 1:

[0240] [ka]

[0241] In the above formula 1, R 1 and R 2 is an ethyl group.

[0242] (5) The titanium nitride (TiN) substrate on which the copper (Cu) pattern was formed was connected to the stainless steel canister so that the substrate could be exposed to the compound represented by Formula 1.

[0243] (6) The chamber was purged with nitrogen gas (N2 gas), and the temperature inside the chamber was maintained at 400°C. The titanium nitride (TiN) substrate having a copper (Cu) pattern formed thereon was exposed to the compound represented by Formula 1 for 30 seconds.

[0244] (7) The titanium nitride (TiN) substrate having the copper (Cu) pattern exposed to the compound represented by Formula 1 was cooled at a temperature of 25°C.

[0245] (8) Using area-selective atomic layer deposition (AS-ALD), a hafnium oxide (HfO2) thin film was formed on a titanium nitride (TiN) substrate with a copper (Cu) pattern exposed to an organic thiol small molecule inhibitor. The compound represented by the following formula 2-1 was used as the thin film deposition precursor, and deionized water was used as the counter reactant.

[0246] [ka]

[0247] In the above chemical formula 2-1, R 3 and R 4is a methyl group.

[0248] Specifically, a stainless-steel canister containing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister containing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a titanium nitride (TiN) substrate with a copper (Cu) pattern. Area-selective atomic layer deposition was performed with the titanium nitride (TiN) substrate with a copper (Cu) pattern heated to 275°C. Nitrogen gas (N2 gas) was used at a flow rate of 10 sccm for purging during area-selective atomic layer deposition, and the flow rate was controlled by a mass flow controller (MFC).

[0249] Meanwhile, the area-selective atomic layer deposition (ALD) process was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a titanium nitride (TiN) substrate with a copper (Cu) pattern, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a titanium nitride (TiN) substrate with a copper (Cu) pattern, exposed for 2 seconds, and then purged for 60 seconds. The ALD process was performed 10 times.

[0250] Comparative Manufacturing Example 1: Formation of a hafnium oxide (HfO2) thin film on a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern

[0251] (1) Silicon dioxide (SiO2) patterns were formed on titanium nitride (TiN) substrates using the drop casting method. The SiO2 patterns were formed using a 0.1M solution of silicon dioxide (SiO2) powder dispersed in 50 ml of ethanol, and the remaining solution after the SiO2 pattern formation was evaporated at 22°C.

[0252] (2) A titanium nitride (TiN) substrate on which a silicon dioxide (SiO2) pattern was formed was ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, in that order, for 10 minutes.

[0253] (3) The cleaned titanium nitride (TiN) substrate with the silicon dioxide (SiO2) pattern formed thereon was dried with nitrogen gas (N2 gas), and then placed in a chamber with an internal temperature of 25°C and maintained for 10 minutes.

[0254] (4) A hafnium oxide (HfO2) thin film was formed on a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern using area selective atomic layer deposition (AS-ALD). The compound represented by the following formula 2-1 was used as the precursor for thin film deposition, and deionized water was used as the counter reactant.

[0255] [ka]

[0256] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0257] Specifically, a stainless-steel canister containing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister containing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern. Area-selective atomic layer deposition was performed with the titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern heated to 275°C. Nitrogen gas (N2 gas) was used for purging at a flow rate of 10 sccm, and the flow rate was controlled by a mass flow controller (MFC).

[0258] Meanwhile, the area-selective atomic layer deposition (ALD) process was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2) pattern, exposed for 2 seconds, and then purged for 60 seconds. The ALD process was performed 10 times.

[0259] Comparative Manufacturing Example 2: Formation of a hafnium oxide (HfO2) thin film on a titanium nitride (TiN) substrate with a copper (Cu) pattern

[0260] (1) A copper (Cu) pattern was formed on a titanium nitride (TiN) substrate using the drop casting method. The copper (Cu) pattern was formed using a 0.1M solution in which copper (Cu) powder was dispersed in 50 ml of ethanol, and the remaining solution after the copper (Cu) pattern formation was evaporated at 22°C.

[0261] (2) The titanium nitride (TiN) substrate on which the copper (Cu) pattern was formed was ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, in that order, for 10 minutes.

[0262] (3) The titanium nitride (TiN) substrate with the cleaned copper (Cu) pattern formed thereon was dried with nitrogen gas (N2 gas), and then placed in a chamber with an internal temperature of 25°C and maintained for 10 minutes.

[0263] (4) A hafnium oxide (HfO2) thin film was formed on a titanium nitride (TiN) substrate with a copper (Cu) pattern by area selective atomic layer deposition (AS-ALD). The compound represented by the following formula 2-1 was used as the precursor for thin film deposition, and deionized water was used as the reactant.

[0264] [ka]

[0265] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0266] Specifically, a stainless-steel canister containing the precursor for thin film deposition, with an internal temperature maintained at 50°C, and a glass canister containing the reactant, with an internal temperature maintained at 22°C, were connected to a chamber containing a titanium nitride (TiN) substrate with a copper (Cu) pattern. Area-selective atomic layer deposition was performed with the titanium nitride (TiN) substrate with a copper (Cu) pattern heated to 275°C. Nitrogen gas (N2 gas) was used at a flow rate of 10 sccm for purging during area-selective atomic layer deposition, and the flow rate was controlled by a mass flow controller (MFC).

[0267] Meanwhile, the area-selective atomic layer deposition (ALD) process was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a titanium nitride (TiN) substrate with a copper (Cu) pattern, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a titanium nitride (TiN) substrate with a copper (Cu) pattern, exposed for 2 seconds, and then purged for 60 seconds. The ALD process was performed 10 times.

[0268] Experimental Example 6: FE-SEM analysis

[0269] The titanium nitride (TiN) substrate with a silicon dioxide (SiO) pattern formed thereon in Preparation Example 1 was analyzed using a field-emission scanning electron microscope (FE-SEM), as shown in Figure 11(a). The titanium nitride (TiN) substrate with a silicon dioxide (SiO) pattern formed thereon in Comparative Preparation Example 1 was analyzed using a field-emission scanning electron microscope (FE-SEM), as shown in Figure 11(b). The titanium nitride (TiN) substrate with a copper (Cu) pattern formed thereon in Preparation Example 2 was analyzed using a field-emission scanning electron microscope, as shown in Figure 11(c). The titanium nitride (TiN) substrate with a copper (Cu) pattern formed thereon in Comparative Preparation Example 2 was analyzed using a field-emission scanning electron microscope, as shown in Figure 11(d). A JEOL JSM-7800F instrument (JEOL Ltd.) was used as the analytical equipment.

[0270] 11(a) and 11(b), it was confirmed that the titanium nitride (TiN) substrate on which the SiO2 pattern was formed in Comparative Preparation Example 1 had greater SiO2 particle roughness than the titanium nitride (TiN) substrate on which the SiO2 pattern was formed in Preparation Example 1, and therefore it was confirmed that a thicker hafnium oxide (HfO2) thin film was formed on the surface of the titanium nitride (TiN) substrate on which the SiO2 pattern was formed in Comparative Preparation Example 1. It was also confirmed that the formation of the hafnium oxide (HfO2) thin film was inhibited on the titanium nitride (TiN) substrate on which the SiO2 pattern was formed in Preparation Example 1 by the adsorbed organic thiol small molecule inhibitor.

[0271] 11(c) and 11(d), it was confirmed that the titanium nitride (TiN) substrate on which the copper (Cu) pattern of Comparative Preparation Example 2 was formed had greater copper (Cu) particle roughness than the titanium nitride (TiN) substrate on which the copper (Cu) pattern of Preparation Example 2 was formed, and therefore it was confirmed that a thicker hafnium oxide (HfO2) thin film was formed on the surface of the titanium nitride (TiN) substrate on which the copper (Cu) pattern of Comparative Preparation Example 2 was formed. It was also confirmed that the formation of the hafnium oxide (HfO2) thin film was inhibited on the titanium nitride (TiN) substrate on which the copper (Cu) pattern of Preparation Example 2 was formed by the adsorbed organic thiol small molecule inhibitor.

[0272] Manufacturing Example 3: Formation of a hafnium oxide (HfO2) thin film on a titanium nitride (TiN) substrate with a silicon dioxide (SiO2)-copper (Cu) pattern

[0273] (1) Silicon dioxide (SiO2)-copper (Cu) patterns were formed on titanium nitride (TiN) substrates using the drop casting method. The silicon dioxide (SiO2)-copper (Cu) patterns were formed using a 0.1M solution of silicon dioxide (SiO2) powder and copper (Cu) powder dispersed in 50 ml of ethanol, and the remaining solution after the formation of the silicon dioxide (SiO2)-copper (Cu) patterns was evaporated at 22°C.

[0274] (2) A titanium nitride (TiN) substrate with a silicon dioxide (SiO2)-copper (Cu) pattern formed thereon was ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, in that order, for 10 minutes.

[0275] (3) The cleaned titanium nitride (TiN) substrate with the silicon dioxide (SiO2)-copper (Cu) pattern formed thereon was dried with nitrogen gas (N2 gas), and then placed in a chamber with an internal temperature of 400°C and a vacuum base pressure, and maintained for 10 minutes.

[0276] (4) A stainless steel canister was prepared, maintaining an internal temperature of 25° C. and storing an organic thiol small molecule inhibitor. The organic thiol small molecule inhibitor used was a compound represented by the following Chemical Formula 1:

[0277] [ka]

[0278] In the above formula 1, R 1 and R 2 is an ethyl group.

[0279] (5) The titanium nitride (TiN) substrate on which the silicon dioxide (SiO)-copper (Cu) pattern was formed was connected to the stainless steel canister so that the substrate could be exposed to the compound represented by Chemical Formula 1.

[0280] (6) The chamber was purged with nitrogen gas (N2 gas), and the temperature inside the chamber was maintained at 400°C. The titanium nitride (TiN) substrate on which the silicon dioxide (SiO2)-copper (Cu) pattern was formed was exposed to the compound represented by Formula 1 for 30 seconds.

[0281] (7) The titanium nitride (TiN) substrate on which the silicon dioxide (SiO2)-copper (Cu) pattern was formed and exposed to the compound represented by Chemical Formula 1 was cooled at a temperature of 25°C.

[0282] (8) Using area-selective atomic layer deposition (AS-ALD), a hafnium oxide (HfO2) thin film was formed on a titanium nitride (TiN) substrate with a silicon dioxide (SiO2)-copper (Cu) pattern exposed to an organic thiol small molecule inhibitor. The compound represented by the following formula 2-1 was used as the thin film deposition precursor, and deionized water was used as the counter reactant.

[0283] [ka]

[0284] In the above chemical formula 2-1, R 3 and R 4 is a methyl group.

[0285] Specifically, a stainless-steel canister containing the precursor for thin film deposition, maintained at an internal temperature of 50°C, and a glass canister containing the reactant, maintained at an internal temperature of 22°C, were connected to a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2)-copper (Cu) pattern. Area-selective atomic layer deposition was performed with the titanium nitride (TiN) substrate with a silicon dioxide (SiO2)-copper (Cu) pattern heated to 275°C. Nitrogen gas (N2 gas) was used for purging at a flow rate of 10 sccm, and the flow rate was controlled by a mass flow controller (MFC).

[0286] Meanwhile, the area-selective atomic layer deposition method was performed in a cycle in which the precursor for thin film deposition was introduced into a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2)-copper (Cu) pattern formed thereon, exposed for 4 seconds, and then purged for 60 seconds, and the reactant was introduced into a chamber containing a titanium nitride (TiN) substrate with a silicon dioxide (SiO2)-copper (Cu) pattern formed thereon, exposed for 2 seconds, and then purged for 60 seconds.

[0287] The area-selective atomic layer deposition was performed 10 times and 25 times, respectively.

[0288] Experimental Example 7: AES analysis

[0289] The titanium nitride (TiN) substrate on which the silicon dioxide (SiO2)-copper (Cu) pattern of Preparation Example 3 was subjected to Auger electron spectroscopy (AES) analysis, and the results are shown in Figure 12. The analysis equipment used was a PHI 700™ Scanning Auger Nanoprobe, and the line scan and mapping methods used a beam size of 20 nm and an analysis area of ​​20 × 20 μm. 2 It is based on a two-point scan.

[0290] Figures 12(a) and 12(d) are AES images of a silicon dioxide (SiO2)-copper (Cu) pattern for a mapping profile and a line scan. Figure 12(b) is a mapping profile after 10 cycles of area-selective atomic layer deposition, and Figure 12(e) is a mapping profile after 25 cycles of area-selective atomic layer deposition. Figure 12(c) is a line scan after 10 cycles of area-selective atomic layer deposition, and Figure 12(f) is a line scan after 25 cycles of area-selective atomic layer deposition.

[0291] Figure 12(b) shows a mapping profile with an RGB overlay of red oxygen (O), green copper (Cu), and blue hafnium (Hf), revealing copper (Cu) patches among the purple patches. The purple patches indicate that oxygen (O) emitted from silicon dioxide (SiO2) and hafnium oxide (HfO2) overlaps with the blue hafnium (Hf). This indicates that no hafnium oxide (HfO2) is present in the copper (Cu) lines of the pattern. These results confirm that complete blocking selectivity of copper (Cu) over silicon dioxide (SiO2) is achieved after 10 cycles of area-selective atomic layer deposition.

[0292] Figure 12(c) shows a line scan of the same pattern, but no hafnium (Hf) concentration was observed in the copper profile (Cu profile), only the oxide profile. The SiO2 line contains oxides contained in SiO2 and hafnium oxide (HfO2), so a larger oxygen (O) intensity was observed in the SiO2 line.

[0293] Meanwhile, hafnium (Hf) was observed in the copper (Cu) lines in Figures 12(e) and (f). These results confirmed that the copper (Cu) lines have hafnium (Hf) blocking properties, interfering with atomic layer deposition. Small green patches can still be observed in Figure 12(e), indicating that the small copper (Cu) patches have not yet covered the hafnium oxide (HfO2). While hafnium (Hf) is present throughout the scanned area in Figure 12(f), even higher hafnium (Hf) concentrations were still observed in the silicon dioxide (SiO2) lines.

[0294] In conclusion, AES analysis confirmed that the organic thiol small molecule inhibitor effectively blocked copper (Cu) up to 10 cycles of area-selective atomic layer deposition on a silicon dioxide (SiO2)-copper (Cu) pattern.

Claims

1. A first substrate containing a metal, a silicon dioxide (SiO ２ a first step of preparing a substrate in which a second substrate including a nitride and a third substrate including a nitride are arranged in parallel; a second step of exposing the substrate to an organothiol small molecule inhibitor; and a third step of forming a thin film on the surface of the substrate exposed to the organothiol small molecule inhibitor using area-selective atomic layer deposition (AS-ALD); The method for selectively depositing a thin film using area-selective atomic layer deposition, wherein the thickness of the thin film formed on the surface of the first substrate, the thickness of the thin film formed on the surface of the second substrate, and the thickness of the thin film formed on the surface of the third substrate are different.

2. the metal is selected from the group consisting of copper (Cu), cobalt (Co), ruthenium (Ru), molybdenum (Mo) and tungsten (W); the nitride is selected from the group consisting of titanium nitride, molybdenum nitride, tungsten nitride, and silicon nitride; 2. The method of claim 1, wherein the thin film is a thin film selected from the group consisting of metals, metal oxides, and silicon dielectric materials.

3. the metal is copper (Cu), the nitride is titanium nitride (TiN); The thin film is made of hafnium oxide (HfO ２ 2. The method for selectively depositing a thin film using area-selective atomic layer deposition according to claim 1, wherein the thin film is a SiO 2 thin film.

4. 2. The method for selectively depositing a thin film using area-selective atomic layer deposition according to claim 1, wherein the following condition (1) is satisfied: (1) A < B < C In the above condition (1), A represents the thickness of the thin film formed on the surface of the first substrate, B represents the thickness of the thin film formed on the surface of the second substrate, and C represents the thickness of the thin film formed on the surface of the third substrate.

5. 2. The method for selectively depositing a thin film using area-selective atomic layer deposition according to claim 1, wherein the organic thiol small molecule inhibitor comprises a compound represented by the following Chemical Formula 1: 【Chemistry 1】 In the above formula 1, R １ and R ２ are each independently a C1 to C12 linear alkyl group, a C3 to C12 branched alkyl group, or a C6 to C12 aryl group.

6. The second stage is Step 2-1: After drying the substrate, the substrate is placed in a chamber having an internal temperature of 300 to 500° C. and a vacuum base pressure, and maintained for 1 to 20 minutes; Step 2-2: purging the chamber, maintaining the chamber internal temperature at 200 to 500° C., introducing an organic thiol small molecule inhibitor into the chamber, and exposing the substrate to the organic thiol small molecule inhibitor for 1 to 100 seconds; and 2. The method for selectively depositing a thin film using area-selective atomic layer deposition according to claim 1, further comprising: a step 2-3 of cooling the substrate exposed to the organic thiol small molecule inhibitor at a temperature of 15 to 35°C.

7. In the second stage the surface of the first substrate exposed to the organic thiol small molecule inhibitor has a water contact angle of 90° to 100°; The method for selectively depositing a thin film using area-selective atomic layer deposition according to claim 1, wherein the surface of the second substrate exposed to the organic thiol small molecule inhibitor has a water contact angle of 70° to 80°.

8. The organic thiol small molecule inhibitor introduced into the chamber is thermally dissociated and separated into alkylsulfanyl and alkyl groups, 7. The method for selectively depositing a thin film using area-selective atomic layer deposition according to claim 6, wherein the alkylsulfanyl is adsorbed on the surface of a first substrate, and the alkyl is adsorbed on the surface of a second substrate.

9. the alkylsulfanyl is ethylsulfanyl, 9. The method of claim 8, wherein the alkyl is ethyl.

10. The third stage is Step 3-1: placing the substrate exposed to the organic thiol small molecule inhibitor into a chamber and heating it to 200 to 350°C; and 2. The method for selectively depositing a thin film using area-selective atomic layer deposition according to claim 1, further comprising: (a) Step 3-2, in which a precursor for thin film deposition is introduced into the chamber, exposed for 1 to 10 seconds, and then purged for 50 to 70 seconds, and a reactant is introduced into the chamber, exposed for 1 to 5 seconds, and then purged for 50 to 70 seconds, to perform area-selective atomic layer deposition in this cycle.

11. 11. The method for selectively depositing a thin film using region-selective atomic layer deposition according to claim 10, wherein the precursor for thin film deposition comprises at least one selected from the group consisting of a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, a compound represented by the following Chemical Formula 4, and a compound represented by the following Chemical Formula 5: [Chemical formula 2] (L １ ) ｎ M(NR ３ R ４ ) ４－ｎ In the above formula 2, L １ is a ligand selected from the group consisting of cyclopentadienyl and C1-C12 alkyl-substituted cyclopentadienyl; M is a metal selected from the group consisting of titanium, hafnium, and zirconium; R ３ and R ４ are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and n is 0, 1, or 2; [Chemical formula 3] R ５ ｍ M(OR ６ ) ３－ｍ In the formula 3, M is a metal selected from the group consisting of aluminum, hafnium, and zirconium; ５ and R ６ are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and m is 1 to 3; [Chemical formula 4] (L ２ ) ｐ MR ７ (OR ８ ) ３－ｐ In the above formula 4, L ２ is a ligand selected from the group consisting of cyclopentadienyl and C1-C12 alkyl-substituted cyclopentadienyl; M is a metal selected from the group consisting of titanium, hafnium, and zirconium; R ７ and R ８ are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group, and p is 1 or 2; [Chemical formula 5] (R ９ N) ｑ M(NR １０ R １１ ) ４－ｑ In the formula 5, M is a metal selected from the group consisting of vanadium, niobium, tantalum, molybdenum, and tungsten; R ９ , R １０ and R １１ are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group; and q is 1 or 2.

12. The compounds represented by Chemical Formula 2 include tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe), ２ ) ３ ), methylcyclopentadienyltris(dimethylamino)hafnium ((MeCp)Hf(NMe ２ ) ３ ), ethylcyclopentadienyltris(dimethylamino)hafnium ((EtCp)Hf(NMe ２ ) ３ ), (n-propylcyclopentadienyl)tris(dimethylamino)hafnium ((n-PrCp)Hf(NMe ２ ) ３ ), cyclopentadienyltris(methylethylamino)hafnium (CpHf(NMeEt) ３ ), methylcyclopentadienyltris(methylethylamino)hafnium ((MeCp)Hf(NMeEt) ３ ), ethylcyclopentadienyltris(methylethylamino)hafnium ((EtCp)Hf(NMeEt) ３ ), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt ２ ) ３ ), methylcyclopentadienyltris(diethylamino)hafnium ((MeCp)Hf(NEt ２ ) ３ ), ethylcyclopentadienyltris(diethylamino)hafnium ((EtCp)Hf(NEt ２ ) ３ ), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp ２ Hf(NMe ２ ) ２ ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) ２ Hf(NMe ２ ) ２ ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) ２ Hf(NMe ２ ) ２ ), bis(cyclopentadienyl)bis(methylethylamino)hafnium (Cp ２ Hf(NMeEt) ２ ), bis(methylcyclopentadienyl)bis(methylethylamino)hafnium ((MeCp) ２ Hf(NMeEt) ２ ), bis(ethylcyclopentadienyl)bis(methylethylamino)hafnium ((EtCp) ２ Hf(NMeEt) ２ ), bis(cyclopentadienyl)bis(diethylamino)hafnium (Cp ２ Hf(NEt ２ ) ２ ), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp) ２ Hf(NEt ２ ) ３ ), bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp) ２ Hf(NEt ２ ) ２ ) or (n-propylcyclopentadienyl)tris(dimethylamino)zirconium ((n-PrCp)Zr(NMe ２ ) ３ ) and The compound represented by Formula 3 is trimethylaluminum, triethylaluminum, dimethylaluminum isopropoxide, or diethylaluminum isopropoxide, The compound represented by Formula 4 is CpHfMe(OMe) ２ , CpZrMe(OMe) ２ , (MeCp)HfMe(OMe) ２ , (MeCp)ZrMe(OMe) ２ , (EtCp)HfMe(OMe) ２ or (EtCp)ZrMe(OMe), The compound represented by Chemical Formula 5 includes tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), tert-butyliminotri(ethylmethylamino)tantalum (TBTEMT), ethyliminotri(diethylamino)tantalum (EITDET), ethyliminotri(dimethylamino)tantalum (EITDMT), ethyliminotri(ethylmethylamino)tantalum (EITEMT), tert-amyliminotri(dimethylamino)tantalum (ETEMT), 12. The method for selectively depositing a thin film using area-selective atomic layer deposition according to claim 11, wherein the compound is thallium (TAIMAT), tert-amyliminotri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amyliminotri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, or bis(tert-butylimino)bis(ethylmethylamino)tungsten.

13. 12. The method of claim 11, wherein the precursor for thin film deposition comprises a compound represented by the following Chemical Formula 2-1: 【Chemistry 2】 In the above chemical formula 2-1, R ３ and R ４ are each independently a C1 to C12 linear alkyl group or a C3 to C12 branched alkyl group.

14. The reactants were deionized water and hydrogen peroxide (H ２ O ２ 11. The method of claim 10, wherein the selective deposition of a thin film using area-selective atomic layer deposition comprises at least one selected from the group consisting of:

15. 11. The method of claim 10, wherein the region-selective atomic layer deposition is performed 2 to 100 times.

16. The area-selective atomic layer deposition method A thin film is formed on the surface of the first substrate with a thickness of 0.3 to 0.8 Å per period; A thin film is formed on the surface of the second substrate with a thickness of 0.8 to 1.5 Å per period; 11. The method of claim 10, wherein a thin film is formed on the surface of the third substrate to a thickness of 1.5 to 2.5 Å per period.

17. A first substrate containing a metal, a silicon dioxide (SiO ２ a substrate in which a second substrate including a nitride and a third substrate including a nitride are arranged in parallel and integrated; and a thin film formed on the surface of the substrate; Alkyl sulfanyl is adsorbed on the surface of the first substrate, and alkyl is adsorbed on the surface of the second substrate, A substrate on which a thin film is selectively formed, wherein the thickness of the thin film formed on the surface of the first substrate, the thickness of the thin film formed on the surface of the second substrate, and the thickness of the thin film formed on the surface of the third substrate are different.

18. 18. The substrate on which a thin film is selectively formed according to claim 17, which satisfies the following condition (1): (1) A < B < C In the above condition (1), A represents the thickness of the thin film formed on the surface of the first substrate, B represents the thickness of the thin film formed on the surface of the second substrate, and C represents the thickness of the thin film formed on the surface of the third substrate.

19. the alkylsulfanyl is ethylsulfanyl, 18. The substrate on which a thin film is selectively formed according to claim 17, wherein the alkyl is ethyl.

20. the metal of the first substrate is copper (Cu); the nitride of the third substrate is titanium nitride (TiN); The thin film is made of hafnium oxide (HfO ２ 18. The substrate on which a thin film is selectively formed according to claim 17, wherein the thin film is a thin film.

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