Precursor for forming lanthanide metal-containing thin film, method for forming lanthanide metal-containing thin film using same, and semiconductor device comprising lanthanide metal-containing thin film

Abstract

The present invention relates to: a precursor for forming a lanthanide metal-containing thin film, the precursor comprising a compound represented by chemical formula 1; a method for forming a lanthanide metal-containing thin film using same; and a semiconductor device comprising the lanthanide metal-containing thin film. The precursor for forming the thin film exhibits the chemical properties of high heat resistance and high volatility by comprising an amidinate ligand, and thus a high-quality thin film may be formed.

Description

A precursor for forming a thin film containing a lanthanide metal, a method for forming a thin film containing a lanthanide metal using the precursor, and a semiconductor device including the thin film containing the lanthanide metal.

[0001] The present invention relates to a precursor for forming a thin film containing a lanthanide metal, a method for forming a thin film containing a lanthanide metal using the same, and a semiconductor device including the thin film containing the lanthanide metal. More specifically, the present invention relates to a precursor for forming a thin film containing a lanthanide metal, which comprises a precursor having high heat resistance and high volatility through a chemical structure including an amidinate ligand, and which can form a high-quality thin film using the precursor, a method for forming a thin film using the same, and a semiconductor device including the thin film.

[0002] As integration increases through miniaturization of semiconductor device line widths, the space available for implementing capacitor structures is constrained by line width. This has led to limitations in the manufacturing methods of semiconductor devices for implementing capacitor structures using existing silicon-based dielectrics. Furthermore, the application of high-k thin films to replace silicon-based dielectrics has led to significant degradation of leakage current due to the bandgap. One solution to this problem requires technology to form high-quality thin films, and for this purpose, it is necessary to optimize the precursors used in thin film formation.

[0003] To this end, various lanthanide metal-containing precursors are being developed. For example, Korean Patent Publication No. 10-2019-0008427 discloses a lanthanide metal-containing precursor containing an aza-allyl ligand, and Korean Patent Publication No. 10-2019-0094238 discloses a lanthanide metal-containing precursor containing a cyclopentadienyl ligand.

[0004] In particular, complex compounds containing a cyclopentathienyl group have lower melting points and higher volatility than compounds containing beta-diketonate or bis(trimethylsilyl)amide, which makes them advantageous for use as precursors in thin film formation processes.

[0005] For this reason, Korean Patent Registration No. 10-1660052, Korean Patent Publication No. 10-2019-0109142, and Korean Patent Publication No. 10-2021-0084297 disclose chemical structures in which cyclopentadienyl and amidinate are bonded as ligands as precursors containing lanthanide metals. These ligand-bonded precursors are reported to be suitable for thin film formation processes because they can improve upon the shortcomings of existing lanthanide metal precursors, such as low vapor pressure and high viscosity.

[0006] It is expected that by applying amidinate ligands to metal-containing precursor compounds from these prior arts, the chemical properties of the precursors can be improved.

[0007] The present invention has been conceived in consideration of the above-described prior arts, and its purpose is to provide a novel lanthanide metal-containing thin film formation precursor capable of exhibiting chemical properties suitable as a thin film formation precursor.

[0008] In addition, the purpose is to provide a precursor for forming a thin film containing a lanthanide metal exhibiting high heat resistance and high volatility chemical properties.

[0009] In addition, the purpose is to provide a method for forming a thin film using the above precursor.

[0010] In addition, the purpose is to provide a semiconductor device including the above thin film.

[0011] To achieve the above purpose, the precursor for forming a thin film containing a lanthanide metal of the present invention is characterized by including a compound represented by the following chemical formula 1.

[0012] [Chemical Formula 1]

[0013]

[0014] In the above chemical formula 1, Ln is a lanthanide metal, R1 and R3 are each independently a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, and R2 is a hydrogen atom or a C1-C8 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0015] In addition, in the above chemical formula 1, R2 may be a hydrogen atom or a C1-C4 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0016] In addition, in the above chemical formula 1, R1 and R3 may each independently be a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0017] Additionally, in the above chemical formula 1, R1 and R3 may be ethyl groups.

[0018] Additionally, in the above chemical formula 1, R2 may be an n-propyl group.

[0019] In addition, in the above chemical formula 1, R1 and R3 may each independently be a C1-C5 straight-chain alkyl group or alkenyl group.

[0020] Additionally, in the above chemical formula 1, R2 may be a C1-C8 straight-chain alkyl group or alkenyl group.

[0021] In addition, in the above chemical formula 1, R1 and R3 are both the same and may be a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0022] Additionally, the precursor for forming the thin film containing the lanthanide metal may be liquid at room temperature.

[0023] In addition, the precursor for forming the thin film may additionally include a solvent, and the solvent may be C1-C 16The solvent may be one or more of a saturated or unsaturated hydrocarbon, a ketone, an ether, a glyme, an ester, tetrahydrofuran, or a tertiary amine. In addition, the solvent may be included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming the thin film.

[0024] In addition, the compounds represented by the above chemical formula 1 may include the following compounds.

[0025] Ln(Me2,H-AMD)3, Ln(Me2,Me-AMD)3, Ln(Me2,Et-AMD)3, Ln(Me2,nPr-AMD)3, Ln(Me2,iPr-AMD)3, Ln(Me2,nBu-AMD)3, Ln(Me2,isoBu-AMD)3, Ln(Me2,secBu-AMD)3, Ln(Me2,tertBu-AMD)3, Ln(Me2,n-pentyl-AMD)3, Ln(Me2,sec-pentyl-AMD)3, Ln(Me2,cylcopentyl-AMD)3, Ln(Me2,n-hexyl-AMD)3, Ln(Et,Me,H-AMD)3, Ln(Et,Me,Me-AMD)3, Ln(Et,Me,Et-AMD)3, Ln(Et,Me,nPr-AMD)3, Ln(Et,Me,iPr-AMD)3, Ln(Et,Me,nBu-AMD)3, Ln(Et,Me,isoBu-AMD)3, Ln(Et,Me,secBu-AMD)3, Ln(Et,Me,tertBu-AMD)3, Ln(Et,Me,n-pentyl-AMD)3, Ln(Et,Me,sec-pentyl-AMD)3, Ln(Et,Me,cylcopentyl-AMD)3, Ln(Et,Me,n-hexyl-AMD)3, Ln(Et2,H-AMD)3, Ln(Et2,Me-AMD)3, Ln(Et2,Et-AMD)3, Ln(Et2,nPr-AMD)3, Ln(Et2,iPr-AMD)3, Ln(Et2,nBu-AMD)3, Ln(Et2,isoBu-AMD)3, Ln(Et2,secBu-AMD)3, Ln(Et2,tertBu-AMD)3, Ln(Et2,n-pentyl-AMD)3, Ln(Et2,sec-pentyl-AMD)3, Ln(Et2,cylcopentyl-AMD)3, Ln(Et2,n-hexyl-AMD)3, Ln(Et,nPr,H-AMD)3, Ln(Et,nPr,Me-AMD)3, Ln(Et,nPr,Et-AMD)3, Ln(Et,nPr,nPr-AMD)3, Ln(Et,nPr,iPr-AMD)3, Ln(Et,nPr,nBu-AMD)3, Ln(Et,nPr,isoBu-AMD)3, Ln(Et,nPr,secBu-AMD)3, Ln(Et,nPr,tertBu-AMD)3,Ln(Et,nPr,n-pentyl-AMD)3, Ln(Et,nPr,sec-pentyl-AMD3, Ln(Et,nPr,cylcopentyl-AMD)3, Ln(Et,nPr,n-hexyl-AMD)3, Ln(nPr,Me,H-AMD)3, Ln(nPr,Me,Me-AMD)3, Ln(nPr,Me,Et-AMD)3, Ln(nPr,Me,nPr-AMD)3, Ln(nPr,Me,iPr-AMD)3, Ln(nPr,Me,nBu-AMD)3, Ln(nPr,Me,isoBu-AMD)3, Ln(nPr,Me,secBu-AMD)3, Ln(nPr,Me,tertBu-AMD)3; Ln(nPr,Me,n-pentyl-AMD)3, Ln(nPr,Me,sec-pentyl-AMD)3, Ln(nPr,Me,cylcopentyl-AMD)3, Ln(nPr,Me,n-hexyl-AMD)3, Ln(nPr2,H-AMD)3, Ln(nPr2,Me-AMD)3, Ln(nPr2,Et-AMD)3, Ln(nPr2,nPr-AMD)3, Ln(nPr2,iPr-AMD)3, Ln(nPr2,nBu-AMD)3, Ln(nPr2,isoBu-AMD)3, Ln(nPr2,secBu-AMD)3, Ln(nPr2,tertBu-AMD)3, Ln(nPr2,n-pentyl-AMD)3, Ln(nPr2,sec-pentyl-AMD)3, Ln(nPr2,cylcopentyl-AMD)3, Ln(nPr2,n-hexyl-AMD)3,

[0026] The method for forming a thin film containing a lanthanide metal of the present invention includes a process of forming a thin film on a substrate using the precursor for forming the thin film, and the process of forming the thin film on the substrate includes a process of forming a precursor thin film by depositing the precursor for forming the thin film on a surface of the substrate, and a process of reacting the precursor thin film with a reactant.

[0027] Additionally, the process of forming the precursor thin film may include a process of vaporizing the precursor for forming the thin film and transporting it into the chamber.

[0028] In addition, the deposition may be performed by any one of a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, a plasma enhanced chemical vapor deposition (PECVD) process, a high density plasma chemical vapor deposition (HDPCVD) process, an atomic layer deposition (ALD) process, or a plasma-enhanced atomic layer deposition (PEALD) process.

[0029] Additionally, the process of forming a thin film on the substrate can be performed at a temperature range of 150 to 500°C.

[0030] Additionally, the reactant may be one or more of nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), oxygen (O2), water vapor (H2O), ozone (O3), hydrogen peroxide (H2O2), silane, hydrogen (H), and diborane (B2H6).

[0031] In addition, the process of forming a thin film containing a lanthanide metal on the substrate may include a step of supplying a precursor for forming the thin film to the substrate and applying plasma to form the thin film.

[0032] In addition, the lanthanide metal-containing thin film of the present invention can be formed using the precursor for forming the thin film, and the semiconductor device of the present invention is characterized by including a thin film manufactured by the method for forming the lanthanide metal-containing thin film.

[0033] The precursor for forming a thin film containing a lanthanide metal according to the present invention has excellent structural stability of the precursor compound by including cyclopentadienyl and amidinate ligands, and exhibits properties such as high volatility and high heat resistance, making it suitable for use in a thin film forming process containing a lanthanide metal.

[0034] In addition, a high-quality lanthanide metal-containing thin film can be formed using the precursor, and a semiconductor device including the lanthanide metal-containing thin film manufactured by the thin film forming method can be provided.

[0035] Figure 1 is a diagram of La(iPr2Me-AMD)3 1 This is the result of H-NMR analysis.

[0036] Figure 2 shows the TGA analysis results of Tb(Et2nPr-AMD)3.

[0037] Figure 3 shows the DSC analysis results of Tb(Et2nPr-AMD)3.

[0038] Figure 4 shows the TGA analysis results of Dy(Et2nPr-AMD)3.

[0039] Figure 5 shows the DSC analysis results of Dy(Et2nPr-AMD)3.

[0040] Figure 6 shows the TGA analysis results of Er(Et2nPr-AMD)3.

[0041] Figure 7 shows the DSC analysis results of Er(Et2nPr-AMD)3.

[0042] Figure 8 shows the TGA analysis results of Yb(Et2nPr-AMD)3.

[0043] Figure 9 is a diagram of Lu(Et2nPr-AMD)3. 1 This is the result of H-NMR analysis.

[0044] Figure 10 shows the TGA analysis results of Lu(Et2nPr-AMD)3.

[0045] Figure 11 shows the DSC analysis results of Lu(Et2nPr-AMD)3.

[0046] The present invention will be described in more detail below. Terms and words used in this specification and claims should not be construed as limited to their conventional or dictionary meanings. Rather, they should be interpreted in a way that is consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of a term to best explain his or her invention.

[0047] The precursor for forming a thin film containing a lanthanide metal according to the present invention is characterized by including a compound represented by the following chemical formula 1.

[0048] [Chemical Formula 1]

[0049]

[0050] In the above chemical formula 1, Ln is a lanthanide metal, R1 and R3 are each independently a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, and R2 is a hydrogen atom or a C1-C8 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0051] The above lanthanide metals include 15 elements including lanthanum (La) with atomic number 57 to lutetium (Lu) with atomic number 71, and may include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

[0052] In the above amidinate ligand, R1 and R3 may be the same or different.

[0053] In addition, R2 constituting the amidinate ligand in the above chemical formula 1 may be a hydrogen atom or a C1-C8 straight-chain, branched or cyclic alkyl group or alkenyl group, and preferably may include an n-alkyl group such as an ethyl group, a propyl group or a butyl group.

[0054] The precursor for forming the above thin film can form various types of compounds depending on the type of functional group.

[0055] In one embodiment, in the above chemical formula 1, R2 may be a hydrogen atom or a C1-C4 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0056] In addition, R1 and R3 can each independently be a C2-C5 straight-chain, branched or cyclic alkyl group or alkenyl group, R1 and R3 can be an ethyl group, and R2 can be an n-propyl group.

[0057] In addition, the above R1 and R3 may each independently be a C1-C5 straight-chain alkyl group or alkenyl group.

[0058] Additionally, in the above chemical formula 1, R2 may be a C1-C8 straight-chain alkyl group or alkenyl group.

[0059] In addition, in the above chemical formula 1, R1 and R3 are both the same and may be a C1-C5 straight-chain, branched or cyclic alkyl group or alkenyl group.

[0060] In addition, the compounds represented by chemical formula 1 that constitute the precursor for forming the above thin film can be exemplified by the following compounds.

[0061] Ln(Me2,H-AMD)3, Ln(Me2,Me-AMD)3, Ln(Me2,Et-AMD)3, Ln(Me2,nPr-AMD)3, Ln(Me2,iPr-AMD)3, Ln(Me2,nBu-AMD)3, Ln(Me2,isoBu-AMD)3, Ln(Me2,secBu-AMD)3, Ln(Me2,tertBu-AMD)3, Ln(Me2,n-pentyl-AMD)3, Ln(Me2,sec-pentyl-AMD)3, Ln(Me2,cylcopentyl-AMD)3, Ln(Me2,n-hexyl-AMD)3, Ln(Et,Me,H-AMD)3, Ln(Et,Me,Me-AMD)3, Ln(Et,Me,Et-AMD)3, Ln(Et,Me,nPr-AMD)3, Ln(Et,Me,iPr-AMD)3, Ln(Et,Me,nBu-AMD)3, Ln(Et,Me,isoBu-AMD)3, Ln(Et,Me,secBu-AMD)3, Ln(Et,Me,tertBu-AMD)3, Ln(Et,Me,n-pentyl-AMD)3, Ln(Et,Me,sec-pentyl-AMD)3, Ln(Et,Me,cylcopentyl-AMD)3, Ln(Et,Me,n-hexyl-AMD)3, Ln(Et2,H-AMD)3, Ln(Et2,Me-AMD)3, Ln(Et2,Et-AMD)3, Ln(Et2,nPr-AMD)3, Ln(Et2,iPr-AMD)3, Ln(Et2,nBu-AMD)3, Ln(Et2,isoBu-AMD)3, Ln(Et2,secBu-AMD)3, Ln(Et2,tertBu-AMD)3, Ln(Et2,n-pentyl-AMD)3, Ln(Et2,sec-pentyl-AMD)3, Ln(Et2,cylcopentyl-AMD)3, Ln(Et2,n-hexyl-AMD)3, Ln(Et,nPr,H-AMD)3, Ln(Et,nPr,Me-AMD)3, Ln(Et,nPr,Et-AMD)3, Ln(Et,nPr,nPr-AMD)3, Ln(Et,nPr,iPr-AMD)3, Ln(Et,nPr,nBu-AMD)3, Ln(Et,nPr,isoBu-AMD)3, Ln(Et,nPr,secBu-AMD)3, Ln(Et,nPr,tertBu-AMD)3,Ln(Et,nPr,n-pentyl-AMD)3, Ln(Et,nPr,sec-pentyl-AMD3, Ln(Et,nPr,cylcopentyl-AMD)3, Ln(Et,nPr,n-hexyl-AMD)3, Ln(nPr,Me,H-AMD)3, Ln(nPr,Me,Me-AMD)3, Ln(nPr,Me,Et-AMD)3, Ln(nPr,Me,nPr-AMD)3, Ln(nPr,Me,iPr-AMD)3, Ln(nPr,Me,nBu-AMD)3, Ln(nPr,Me,isoBu-AMD)3, Ln(nPr,Me,secBu-AMD)3, Ln(nPr,Me,tertBu-AMD)3; Ln(nPr,Me,n-pentyl-AMD)3, Ln(nPr,Me,sec-pentyl-AMD)3, Ln(nPr,Me,cylcopentyl-AMD)3, Ln(nPr,Me,n-hexyl-AMD)3, Ln(nPr2,H-AMD)3, Ln(nPr2,Me-AMD)3, Ln(nPr2,Et-AMD)3, Ln(nPr2,nPr-AMD)3, Ln(nPr2,iPr-AMD)3, Ln(nPr2,nBu-AMD)3, Ln(nPr2,isoBu-AMD)3, Ln(nPr2,secBu-AMD)3, Ln(nPr2,tertBu-AMD)3, Ln(nPr2,n-pentyl-AMD)3, Ln(nPr2,sec-pentyl-AMD)3, Ln(nPr2,cylcopentyl-AMD)3, Ln(nPr2,n-hexyl-AMD)3,

[0062] The compound represented by the above chemical formula 1 is a precursor containing an amidinate ligand with a lanthanide metal as a central metal atom, has high thermal stability and volatility, and can have a liquid form at room temperature, so that the chemical properties of the desired precursor can be obtained through the synthesis of a precursor containing the ligand.

[0063] Specifically, the precursor for forming the thin film may be liquid at room temperature.

[0064] The chemical structure of these precursors for thin film formation enables the production of liquid precursors with high heat resistance and high volatility, thereby enabling the formation of high-quality thin films.

[0065] In addition, the precursor for forming a thin film of the present invention may additionally include a solvent for dissolving or diluting the precursor compound, taking into consideration the conditions and efficiency of the thin film forming process. The solvent may be C1-C 16 Any one or a mixture of saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines may be used. The C1-C 16 Examples of saturated or unsaturated hydrocarbons include toluene and heptane, and examples of tertiary amines include dimethylethylamine.

[0066] In particular, depending on the chemical structure, the compound of the precursor for forming a thin film may be in a solid state at room temperature, in which case the compound can be dissolved by including the solvent. That is, when the solvent is included, the solvent is included in an amount capable of dissolving the precursor compound, and it is preferably included in an amount of 1 to 99 wt% based on the total weight of the precursor for forming a thin film.

[0067] Since the precursor, which may or may not contain the above solvent, is vaporizable, it can be supplied into the chamber in the form of a precursor gas. Accordingly, depending on the type of precursor compound for thin film formation, if it exists in a liquid state at room temperature and can be easily vaporized, the thin film formation process can be performed without a separate solvent.

[0068] In addition, the lanthanide metal-containing thin film formation process may be performed by any one of a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, a plasma enhanced chemical vapor deposition (PECVD) process, a high density plasma chemical vapor deposition (HDPCVD) process, an atomic layer deposition (ALD) process, or a plasma-enhanced atomic layer deposition (PEALD) process.

[0069] For example, when the HDP-CVD process is applied, it can be performed under high vacuum and high power compared to the atmospheric pressure chemical vapor deposition process (AP-CVD), low pressure chemical vapor deposition process (LP-CVD), or plasma enhanced chemical vapor deposition process (PE-CVD), so it is possible to form a thin film that is structurally dense and has excellent mechanical properties.

[0070] To this end, the thin film forming method according to the present invention includes a process of forming a thin film on a substrate using the precursor for forming the thin film.

[0071] Specifically, the process for forming a lanthanide-containing thin film on the substrate may include a process for forming a precursor thin film by depositing a precursor for forming the thin film on the surface of the substrate and a process for reacting the precursor thin film with a reactant.

[0072] In addition, a process of vaporizing the precursor for forming the thin film and transporting it into the chamber for deposition of the precursor may be included.

[0073] In addition, the process of forming a thin film containing a lanthanide metal on the substrate may include a process of forming a thin film of a metal, oxide, nitride, oxynitride, etc. by supplying a precursor for forming the thin film to the substrate and applying plasma in the presence of a reactant.

[0074] The process of forming the above thin film can be performed under chamber pressure conditions of 1 to 1,000 mTorr. In addition, the source power for forming plasma within the chamber is appropriately 500 to 9,000 W, and the bias power is appropriately 0 to 5,000 W. In addition, the bias power may not be applied in some cases.

[0075] Additionally, the process of forming a thin film on the substrate can be performed at a temperature range of 150 to 500°C.

[0076] In addition, when supplying the precursor for forming the above thin film, a second metal precursor may be introduced as needed to further improve the electrical characteristics of the finally formed metal film, i.e., the electrostatic capacity or leakage current value. The second metal precursor may optionally further supply a metal precursor including at least one metal (M") selected from silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta), and actinide (Ac) atoms. The second metal precursor may be an alkylamide compound or an alkoxy compound including the metal. For example, when the metal is Si, SiH(N(CH3)2)3, Si(N(C2H5)2)4, Si(N(C2H5)(CH3))4, Si(N(CH3)2)4, Si(OC4H9)4, Si(OC2H5)4, Si(OCH3)4, Si(OC(CH3)3)4, etc. may be used as the second metal precursor.

[0077] The supply of the second metal precursor may be performed in the same manner as the supply method of the precursor for forming the thin film, and the second metal precursor may be supplied onto the substrate for forming the thin film together with the precursor, or may be supplied sequentially after the supply of the precursor is completed.

[0078] It is preferable that the precursor for forming a thin film as described above and optionally the second metal precursor be maintained at a temperature of 50 to 250°C, more preferably 100 to 200°C, before being supplied into the reaction chamber to contact the substrate for forming the thin film.

[0079] In addition, after the precursor supply step and prior to the supply of the reactant, a process of purging the inside of the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) may be performed to assist the movement of the precursor and optionally the second metal precursor onto the substrate, to ensure that the inside of the reactor has an appropriate pressure for deposition, and to discharge impurities, etc., existing in the chamber to the outside. At this time, the purging of the inert gas is preferably performed so that the pressure inside the reactor becomes 1 to 5 Torr.

[0080] In addition, any one or more of nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), oxygen (O2), water vapor (H2O), ozone (O3), hydrogen peroxide (H2O2), silane, hydrogen (H), and diborane (B2H6) may be used as the reactants. When carried out in the presence of an oxidizing gas such as water vapor, oxygen, or ozone, a magnesium oxide thin film may be formed, and when carried out in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, or silane, a thin film of a metal monolayer or metal nitride may be formed. In addition, a metal oxynitride thin film may also be formed by mixing the reactants.

[0081] In addition to plasma treatment, a heat treatment or photo-irradiation treatment process may also be performed. This process provides thermal energy for the deposition of precursors for forming thin films, and can be performed using conventional methods. Preferably, the treatment process is performed so that the temperature of the substrate within the reactor is 100 to 1,000°C, preferably 250 to 400°C, to produce a thin film having the desired physical state and composition at a sufficient growth rate.

[0082] In addition, during the above treatment process, as described above, a process of purging the reactor with an inert gas such as argon (Ar), nitrogen (N2), or helium (He) may be performed in order to help the reactants move onto the substrate, to ensure that the reactor has an appropriate pressure for deposition, and to discharge impurities or byproducts existing in the reactor to the outside.

[0083] The above process of introducing a precursor for forming a thin film, introducing a reactant, and introducing an inert gas is considered one cycle. By repeating this process for one or more cycles, a thin film can be formed.

[0084] In addition, by applying the above thin film formation process, various semiconductor devices including thin films can be manufactured.

[0085] Hereinafter, the effects of the present invention will be explained through examples.

[0086] [Comparative Example 1] Synthesis of tris-(diisopropyl-methylamidinato)lanthanum [La(iPr2Me-AMD)3]

[0087] Into a 500-mL Schlenk flask, add 20.0 g (0.0815 mol) of LaCl3 and 160 ml of THF, and stir at room temperature for 4 hours. Into a 500-mL Schlenk flask, add 80 ml of THF and 155.5 ml (0.2487 mol) of MeLi-diethyl ether solution (1.6 M), cool to -78°C, slowly add 30.86 g (0.2446 mol) of 1,3-diisopropylcarbodiimide dropwise, and stir at room temperature for 6 hours to prepare Li-(iPr2Me-AMD). The prepared Li-(iPr2Me-AMD) solution was added dropwise to a flask containing 20.0 g (0.0815 mol) of LaCl3 at 0°C, and stirred at room temperature for 12 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 260°C and 150 mTorr to obtain a light yellow solid. The yield was 25.1 g (54.7%).

[0088] Fig. 1 1 From the H-NMR (Bruker AV400MHz HD) analysis results, it was confirmed that a lanthanide metal compound of the following chemical formula 1-1 was synthesized.

[0089] [Chemical Formula 1-1]

[0090]

[0091] [Example 1] Synthesis of tris-(diethyl-n-propylamidinato)terbium [Tb(Et2nPr-AMD)3]

[0092] Into a 500-mL Schlenk flask, add 10.0 g (0.0377 mol) of TbCl3 and 50 ml of THF, and stir at room temperature for 4 hours. Into a 250-mL Schlenk flask, add 50 ml of THF and 16.1 g (0.114 mol) of diethyl-n-propylamidinate, cool to -78°C, and slowly add 47.5 ml (0.119 mol) of n-BuLi-hexane solution (2.5 M) dropwise, and stir at room temperature for 2 hours to prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0377 mol) of TbCl3 at 0°C, and stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 138 mTorr to obtain a yellow liquid. The yield was 11.0 g (50.1%), and the resulting compound was identified as a lanthanide metal compound of the following chemical formula 1-2.

[0093] [Chemical Formula 1-2]

[0094]

[0095] The yellow liquid left almost no residual mass, 1.18%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed from the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 2.

[0096] Additionally, a yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 417°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min. This result was confirmed from the DSC analysis results showing the change in thermal energy according to the temperature change in Fig. 3.

[0097] [Example 2] Synthesis of tris-(diethyl-n-propylamidinato)diceprosium [Dy(Et2nPr-AMD)3]

[0098] Into a 500-mL Schlenk flask, add 10.0 g (0.0372 mol) of DyCl3 and 50 ml of THF, and stir at room temperature for 4 hours. Into a 250-mL Schlenk flask, add 50 ml of THF and 15.9 g (0.112 mol) of diethyl-n-propylamidinate, cool to -78°C, and slowly add 46.9 ml (0.117 mol) of n-BuLi-hexane solution (2.5 M) dropwise, and stir at room temperature for 2 hours to prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0372 mol) of DyCl3 at 0°C, and stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 90 mTorr to obtain a yellow liquid. The yield was 13.8 g (69%), and the resulting compound was identified as a lanthanide metal compound of the following chemical formula 1-3.

[0099] [Chemical Formula 1-3]

[0100]

[0101] The yellow liquid left almost no residual mass, 1.59%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed from the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 4.

[0102] Additionally, a yellow liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 487°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min. This result was confirmed from the DSC analysis results showing the change in thermal energy according to the temperature change in Fig. 5.

[0103] [Example 3] Synthesis of tris-(diethyl-n-propylamidinato)erbium [Er(Et2nPr-AMD)3]

[0104] Into a 500-mL Schlenk flask, 10.0 g (0.0365 mol) of ErCl3 and 50 ml of THF were added, and the mixture was stirred at room temperature for 4 hours. Into a 250-mL Schlenk flask, 50 ml of THF and 15.6 g (0.110 mol) of diethyl-n-propylamidinate were added, and after cooling to -78°C, 46.0 ml (0.115 mol) of n-BuLi-hexane solution (2.5 M) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours to prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0365 mol) of ErCl3 at 0°C, and the mixture was stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 80 mTorr to obtain an orange liquid. The yield was 14 g (72%), and the resulting compound was identified as a lanthanide metal compound of the following chemical formula 1-4.

[0105] [Chemical Formula 1-4]

[0106]

[0107] The orange liquid left almost no residual mass, 1.52%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 6.

[0108] Additionally, an orange liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 466°C during DSC (TA instrument Discovery 25) analysis measured at a temperature ramp rate of 10°C / min. This result was confirmed from the DSC analysis results showing the change in thermal energy according to the temperature change in Fig. 7.

[0109] In addition, to check the viscosity of the orange liquid, a sample was placed in the measuring container of a rotational viscometer (Brookfield LVD2T) and the viscosity was measured using a low-viscosity spindle at 25°C, and it was confirmed to be 77.1 cPs.

[0110] [Example 4] Synthesis of tris-(diethyl-n-propylamidinato)ytterbium [Yb(Et2nPr-AMD)3]

[0111] Into a 500-mL Schlenk flask, 10.0 g (0.0358 mol) of YbCl3 and 50 ml of THF were added, and the mixture was stirred at room temperature for 4 hours. Into a 250-mL Schlenk flask, 50 ml of THF and 15.3 g (0.107 mol) of diethyl-n-propylamidinate were added, and after cooling to -78°C, 45.1 ml (0.113 mol) of n-BuLi-hexane solution (2.5 M) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours to prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0358 mol) of YbCl3 at 0°C, and the mixture was stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 68 mTorr to obtain a yellow liquid. The yield was 14 g (70%), and the resulting compound was identified as a lanthanide metal compound of the following chemical formula 1-5.

[0112] [Chemical Formula 1-5]

[0113]

[0114] The yellow liquid left almost no residual mass, 1.68%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature rise rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed from the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 8.

[0115] In addition, to check the viscosity of the yellow liquid, a sample was placed in the measuring container of a rotational viscometer (Brookfield LVD2T) and the viscosity was measured with a low-viscosity spindle at 25°C, and was shown at 66.2 cPs.

[0116] [Example 5] Synthesis of tris-(diethyl-n-propylamidinato)lutetium [Lu(Et2nPr-AMD)3]

[0117] Into a 500-mL Schlenk flask, 10.0 g (0.0355 mol) of LuCl3 and 50 ml of THF were added, and the mixture was stirred at room temperature for 4 hours. Into a 250-mL Schlenk flask, 50 ml of THF and 15.2 g (0.107 mol) of diethyl-n-propylamidinate were added, and after cooling to -78°C, 44.8 ml (0.112 mol) of n-BuLi-hexane solution (2.5 M) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours to prepare Li-(Et2nPr-AMD). The prepared Li-(Et2nPr-AMD) solution was added dropwise to a flask containing 10 g (0.0355 mol) of LuCl3 at 0°C, and the mixture was stirred at room temperature for 6 hours. The mixture was filtered, the solvent and volatiles were evaporated under vacuum, and distilled at 220°C and 54 mTorr to obtain an orange liquid. The yield was 16.2 g (75.8%).

[0118] Of the above compounds 1 The results of H-NMR (Bruker AV400MHz HD) analysis are as shown in Fig. 9, and it was confirmed that a lanthanide metal compound of the following chemical formula 1-6 was synthesized from the characteristic peaks of 0.88 (t, 9H), 1.30 (t, 18H), 1.51 (q, 6H), 2.21 (q, 6H), and 3.28 (q, 12H).

[0119] [Chemical Formula 1-6]

[0120]

[0121] The orange liquid left almost no residual mass, 0.95%, during TGA (TA Instruments SDT Q600) analysis measured at a temperature ramp rate of 10°C / min in an atmosphere flowing nitrogen at 200 ml / min. This result was confirmed by the TGA analysis results showing the weight loss percentage according to temperature change in Fig. 10.

[0122] Additionally, an orange liquid sample was placed in a sealed container for DSC and maintained at 40°C for 10 minutes, and a decomposition peak was observed at 442°C during DSC analysis (TA instrument Discovery 25) measured at a temperature ramp rate of 10°C / min. This result was confirmed from the DSC analysis results showing the change in thermal energy according to temperature change in Fig. 11.

[0123] While the present invention has been described with reference to preferred embodiments as described above, it is not limited to the above embodiments, and various modifications and variations are possible by those skilled in the art without departing from the spirit of the invention. Such modifications and variations are deemed to fall within the scope of the present invention and the appended claims.

Claims

1. A precursor for forming a thin film containing a lanthanide metal, characterized in that it comprises a lanthanide metal-containing compound represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, Ln is a lanthanide metal, R 1 and R 3 are each independently C 1 -C 5 A straight-chain, branched or cyclic alkyl or alkenyl group, R 2 is a hydrogen atom or C 1 -C 8 is a straight-chain, branched or cyclic alkyl or alkenyl group.

2. In claim 1, In the chemical formula 1 above, R 2 is a hydrogen atom or C 1 -C 4 A precursor for forming a thin film containing a lanthanide metal, characterized in that the precursor is a straight-chain, branched or cyclic alkyl group or alkenyl group.

3. In claim 1, In the chemical formula 1 above, R 1 and R 3 are each independently C 2 -C 5 A precursor for forming a thin film containing a lanthanide metal, characterized in that the precursor is a straight-chain, branched or cyclic alkyl group or alkenyl group.

4. In claim 1, In the chemical formula 1 above, R 1 and R 3 A precursor for forming a thin film containing a lanthanide metal, characterized in that it is an ethyl group.

5. In claim 1, In the chemical formula 1 above, R 2 A precursor for forming a thin film containing a lanthanide metal, characterized in that it is an n-propyl group.

6. In claim 1, In the chemical formula 1 above, R 1 and R 3 are each independently C 1 -C 5 A precursor for forming a thin film containing a lanthanide metal, characterized by having a straight-chain alkyl group or alkenyl group.

7. In claim 1, In the chemical formula 1 above, R 2 is C 1 -C 8 A precursor for forming a thin film containing a lanthanide metal, characterized by having a straight-chain alkyl group or alkenyl group.

8. In claim 1, In the chemical formula 1 above, R 1 and R 3 are all the same, C 1 -C 5 A precursor for forming a thin film containing a lanthanide metal, characterized in that the precursor is a straight-chain, branched or cyclic alkyl group or alkenyl group.

9. In claim 1, A precursor for forming a thin film containing a lanthanide metal, characterized in that the precursor for forming a thin film containing a lanthanide metal is liquid at room temperature.

10. In claim 1, A precursor for forming a thin film containing a lanthanide metal, characterized in that the precursor for forming the thin film additionally contains a solvent.

11. In claim 10, The above solvent is C 1 -C 16 A precursor for forming a thin film containing a lanthanide metal, characterized in that it is one or more of a saturated or unsaturated hydrocarbon, a ketone, an ether, a glyme, an ester, tetrahydrofuran, and a tertiary amine.

12. In claim 10, A precursor for forming a thin film containing a lanthanide metal, characterized in that the solvent is contained in an amount of 1 to 99 wt% based on the total weight of the precursor for forming a thin film.

13. In claim 1, A precursor for forming a thin film, characterized in that the lanthanide metal-containing compound represented by the above chemical formula 1 is at least one selected from the following compounds. Ln(Me 2 ,H-AMD) 3 , Ln(Me 2 ,Me-AMD) 3 , Ln(Me 2 ,Et-AMD) 3 , Ln(Me 2 ,nPr-AMD) 3 , Ln(Me 2 ,iPr-AMD) 3 , Ln(Me 2 ,nBu-AMD) 3 , Ln(Me 2 ,isoBu-AMD) 3 , Ln(Me 2 ,secBu-AMD) 3 , Ln(Me 2 ,tertBu-AMD) 3 , Ln(Me 2 ,n-pentyl-AMD) 3 , Ln(Me 2 ,sec-pentyl-AMD) 3 , Ln(Me 2 ,cylcopentyl-AMD) 3 , Ln(Me 2 ,n-hexyl-AMD) 3 , Ln(Et,Me,H-AMD) 3 , Ln(Et,Me,Me-AMD) 3 , Ln(Et,Me,Et-AMD) 3 , Ln(Et,Me,nPr-AMD) 3 , Ln(Et,Me,iPr-AMD) 3 , Ln(Et,Me,nBu-AMD) 3 , Ln(Et,Me,isoBu-AMD) 3 , Ln(Et,Me,secBu-AMD) 3 , Ln(Et,Me,tertBu-AMD) 3 , Ln(Et,Me,n-pentyl-AMD) 3 , Ln(Et,Me,sec-pentyl-AMD) 3 , Ln(Et,Me,cylcopentyl-AMD) 3 , Ln(Et,Me,n-hexyl-AMD) 3 , Ln(Et 2 ,H-AMD) 3 , Ln(Et 2 ,Me-AMD) 3 , Ln(Et 2 ,Et-AMD) 3 , Ln(Et 2 ,nPr-AMD) 3 , Ln(Et 2 ,iPr-AMD) 3 , Ln(Et 2 ,nBu-AMD) 3 , Ln(Et 2 ,AMD eye) 3 , Ln(Et 2 ,secBu-AMD) 3 , Ln(Et 2 ,tertBu-AMD) 3 , Ln(Et 2 ,n-pencil-AMD) 3 , Ln(Et 2 ,sec-paint-AMD) 3 , Ln(Et 2 ,cylcopentyl-AMD) 3 , Ln(Et 2 ,n-hexyl-AMD) 3 , Ln(Et,nPr,H-AMD) 3 , Ln(Et,nPr,Me-AMD) 3 , Ln(Et,nPr,Et-AMD) 3 , Ln(Et,nPr,nPr-AMD) 3 , Ln(Et,nPr,iPr-AMD) 3 , Ln(Et,nPr,nBu-AMD) 3 , Ln(Et,nPr,isoBu-AMD) 3 , Ln(Et,nPr,secBu-AMD) 3 , Ln(Et,nPr,tertBu-AMD) 3 , Ln(Et,nPr,n-pentyl-AMD) 3 , Ln(Et,nPr,sec-pentyl-AMD 3 , Ln(Et,nPr,cylcopentyl-AMD) 3 , Ln(Et,nPr,n-hexyl-AMD) 3 , Ln(nPr,Me,H-AMD) 3 , Ln(nPr,Me,Me-AMD) 3 , Ln(nPr,Me,Et-AMD) 3 , Ln(nPr,Me,nPr-AMD) 3 , Ln(nPr,Me,iPr-AMD) 3 , Ln(nPr,Me,nBu-AMD) 3 , Ln(nPr,Me,isoBu-AMD) 3 , Ln(nPr,Me,secBu-AMD) 3 , Ln(nPr,Me,tertBu-AMD) 3 , Ln(nPr,Me,n-pentyl-AMD) 3 , Ln(nPr,Me,sec-pentyl-AMD) 3 , Ln(nPr,Me,cylcopentyl-AMD) 3 , Ln(nPr,Me,n-hexyl-AMD) 3 , Ln(nPr 2 ,H-AMD) 3 , Ln(nPr 2 ,Me-AMD) 3 , Ln(nPr 2 ,Et-AMD) 3 , Ln(nPr 2 ,nPr-AMD) 3 , Ln(nPr 2 ,iPr-AMD) 3 , Ln(nPr 2 ,nBu-AMD) 3 , Ln(nPr 2 ,isoBu-AMD) 3 , Ln(nPr 2 ,secBu-AMD) 3 , Ln(nPr 2 ,tertBu-AMD) 3 , Ln(nPr 2 ,n-pentyl-AMD) 3 , Ln(nPr 2 ,sec-pentyl-AMD) 3 , Ln(nPr 2 ,cylcopentyl-AMD) 3 , Ln(nPr 2 ,n-hexyl-AMD) 3 14. A method for forming a thin film containing a lanthanide metal, characterized by including a process for forming a thin film on a substrate using a precursor for forming a thin film according to claim 1 or 10.

15. In claim 14, The process of forming a thin film on the above substrate is: A process for forming a precursor thin film by depositing the precursor for forming the thin film on the surface of a substrate; A process of reacting the above precursor thin film with a reactive gas; A method for forming a thin film containing a lanthanide metal, characterized by including:

16. In claim 15, A method for forming a thin film containing a lanthanide metal, characterized in that the process for forming the precursor thin film includes a process of vaporizing the precursor for forming the thin film and transporting it into the chamber.

17. In claim 15, A method for forming a lanthanide metal-containing thin film, characterized in that the deposition is performed by any one of a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, a plasma enhanced chemical vapor deposition (PECVD) process, a high density plasma -chemical vapor deposition (HDPCVD) process, an atomic layer deposition (ALD) process, or a plasma-enhanced atomic layer deposition (PEALD) process.

18. In claim 14, The process of forming a thin film on the above substrate is: A method for forming a thin film containing a lanthanide metal, characterized by including a step of supplying a precursor for forming the thin film to a substrate and applying plasma to form a thin film.

19. A semiconductor device characterized by including a lanthanide metal-containing thin film manufactured by the thin film forming method of claim 14.

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