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

Proposed are a precursor for forming a lanthanide metal-containing thin film, the precursor including a compound represented by Chemical Formula 1, a method for forming a lanthanide metal-containing thin film using the same, and a semiconductor device including the lanthanide metal-containing thin film. The precursor for forming the thin film contains an amidinate ligand and thus exhibits chemical properties, such as high heat resistance and high volatility, thereby enabling the formation of a high-quality thin film.

Claims

1. A precursor for forming a lanthanide metal-containing thin film, the precursor comprising a lanthanide metal-containing compound represented by Chemical Formula 1 below, ##STR00009## wherein in Chemical Formula 1, Ln refers to a lanthanide metal, R.sub.1 and R.sub.5 are each independently a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 1 to 5 carbon atoms, and R.sub.2 is a hydrogen atom, or a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 1 to 8 carbon atoms.

2. The precursor of claim 1, wherein in Chemical Formula 1, R.sub.2 is a hydrogen atom, or a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 1 to 4 carbon atoms.

3. The precursor of claim 1, wherein in Chemical Formula 1, R.sub.1 and R.sub.3 are each independently a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 2 to 5 carbon atoms.

4. The precursor of claim 1, wherein in Chemical Formula 1, R.sub.1 and R.sub.3 are ethyl groups.

5. The precursor of claim 1, wherein in Chemical Formula 1, R.sub.2 is an n-propyl group.

6. The precursor of claim 1, wherein in Chemical Formula 1, R.sub.1 and R.sub.3 are each independently a straight-chain alkyl or alkenyl group having 1 to 5 carbon atoms.

7. The precursor of claim 1, wherein in Chemical Formula 1, R.sub.2 is a straight-chain alkyl or alkenyl group having 1 to 8 carbon atoms.

8. The precursor of claim 1, wherein in Chemical Formula 1, R.sub.1 and R.sub.3 are both the same, and are straight-chain, branched-chain, or cyclic alkyl or alkenyl groups having 1 to 5 carbon atoms.

9. The precursor of claim 1, wherein the precursor is liquid at room temperature.

10. The precursor of claim 1, further comprising a solvent.

11. The precursor of claim 10, wherein the solvent comprises one or more of the following: a saturated or unsaturated hydrocarbon having 1 to 16 carbon atoms, a ketone, an ether, glyme, an ester, tetrahydrofuran, and a tertiary amine.

12. The precursor of claim 10, wherein the solvent is included in an amount in a range of 1 to 99 wt % with respect to the total weight of the precursor.

13. The precursor of claim 1, wherein the lanthanide metal-containing compound represented by Chemical Formula 1 comprises at least one selected from the following compounds: Ln(Me.sub.2,H-AMD).sub.3, Ln(Me.sub.2,Me-AMD).sub.3, Ln(Me.sub.2,Et-AMD).sub.3, Ln(Me.sub.2,nPr-AMD).sub.3, Ln(Me.sub.2,iPr-AMD).sub.3, Ln(Me.sub.2,nBu-AMD).sub.3, Ln(Me.sub.2,isoBu-AMD).sub.3, Ln(Me.sub.2,secBu-AMD).sub.3, Ln(Me.sub.2,tertBu-AMD).sub.3, Ln(Me.sub.2,n-pentyl-AMD).sub.3, Ln(Me.sub.2,sec-pentyl-AMD).sub.3, Ln(Me.sub.2,cyclopentyl-AMD).sub.3, Ln(Me.sub.2,n-hexyl-AMD).sub.3, Ln(Et,Me,H-AMD).sub.3, Ln(Et,Me,Me-AMD).sub.3, Ln(Et,Me,Et-AMD).sub.3, Ln(Et,Me,nPr-AMD).sub.3, Ln(Et,Me,iPr-AMD).sub.3, Ln(Et,Me,nBu-AMD).sub.3, Ln(Et,Me,isoBu-AMD).sub.3, Ln(Et,Me,secBu-AMD).sub.3, Ln(Et,Me,tertBu-AMD).sub.3, Ln(Et,Me,n-pentyl-AMD).sub.3, Ln(Et,Me,sec-pentyl-AMD).sub.3, Ln(Et,Me,cyclopentyl-AMD).sub.3, Ln(Et,Me,n-hexyl-AMD).sub.3, Ln(Et.sub.2,H-AMD).sub.3, Ln(Et.sub.2,Me-AMD).sub.3, Ln(Et.sub.2,Et-AMD).sub.3, Ln(Et.sub.2,nPr-AMD).sub.3, Ln(Et.sub.2,iPr-AMD).sub.3, Ln(Et.sub.2,nBu-AMD).sub.3, Ln(Et.sub.2,isoBu-AMD).sub.3, Ln(Et.sub.2,secBu-AMD).sub.3, Ln(Et.sub.2,tertBu-AMD).sub.3, Ln(Et.sub.2,n-pentyl-AMD).sub.3, Ln(Et.sub.2, sec-pentyl-AMD).sub.3, Ln(Et.sub.2,cyclopentyl-AMD).sub.3, Ln(Et.sub.2,n-hexyl-AMD).sub.3, Ln(Et,nPr,H-AMD).sub.3, Ln(Et,nPr,Me-AMD).sub.3, Ln(Et,nPr,Et-AMD).sub.3, Ln(Et,nPr,nPr-AMD).sub.3, Ln(Et,nPr,iPr-AMD).sub.3, Ln(Et,nPr,nBu-AMD).sub.3, Ln(Et,nPr,isoBu-AMD).sub.3, Ln(Et,nPr,secBu-AMD).sub.3, Ln(Et,nPr,tertBu-AMD).sub.3, Ln(Et,nPr,n-pentyl-AMD).sub.3, Ln(Et,nPr,sec-pentyl-AMD).sub.3, Ln(Et,nPr,cyclopentyl-AMD).sub.3, Ln(Et,nPr,n-hexyl-AMD).sub.3, Ln(nPr,Me,H-AMD).sub.3, Ln(nPr,Me,Me-AMD).sub.3, Ln(nPr,Me,Et-AMD).sub.3, Ln(nPr,Me,nPr-AMD).sub.3, Ln(nPr,Me,iPr-AMD).sub.3, Ln(nPr,Me,nBu-AMD).sub.3, Ln(nPr,Me,isoBu-AMD).sub.3, Ln(nPr,Me,secBu-AMD).sub.3, Ln(nPr,Me,tertBu-AMD).sub.3, Ln(nPr,Me,n-pentyl-AMD).sub.3, Ln(nPr,Me,sec-pentyl-AMD).sub.3, Ln(nPr,Me,cyclopentyl-AMD).sub.3, Ln(nPr,Me,n-hexyl-AMD).sub.3, Ln(nPr.sub.2,H-AMD).sub.3, Ln(nPr.sub.2,Me-AMD).sub.3, Ln(nPr.sub.2,Et-AMD).sub.3, Ln(nPr.sub.2,nPr-AMD).sub.3, Ln(nPr.sub.2,iPr-AMD).sub.3, Ln(nPr.sub.2,nBu-AMD).sub.3, Ln(nPr.sub.2,isoBu-AMD).sub.3, Ln(nPr.sub.2,secBu-AMD).sub.3, Ln(nPr.sub.2, tertBu-AMD).sub.3, Ln(nPr.sub.2,n-pentyl-AMD).sub.3, Ln(nPr.sub.2,sec-pentyl-AMD).sub.3, Ln(nPr.sub.2,cyclopentyl-AMD).sub.3, and Ln(nPr.sub.2,n-hexyl-AMD).sub.3.

14. A method for forming a lanthanide metal-containing thin film, the method comprising forming a thin film on a substrate using the precursor of claim 1.

15. The method of claim 14, wherein the forming of the thin film on the substrate comprises: forming a precursor thin film through deposition of the precursor onto a surface of the substrate; and reacting the precursor thin film with a reactive gas.

16. The method of claim 15, wherein the forming of the precursor thin film comprises vaporizing the precursor so as to transfer the resulting vapor of the precursor into a chamber.

17. The method of claim 15, wherein the deposition is performed by any one of the following: a spin-on dielectric (SOD) process, a low-temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, a plasma-enhanced CVD (PECVD) process, a high-density plasma CVD (HDPCVD) process, an atomic layer deposition (ALD) process, or a plasma-enhanced ALD (PEALD) process.

18. The method of claim 14, wherein the forming of the thin film on the substrate comprises feeding the precursor onto the substrate and applying a plasma, thereby forming the thin film.

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

Description

DESCRIPTION OF DRAWINGS

[0033] FIG. 1 shows the proton nuclear magnetic resonance (1H-NMR) result of La(iPr.sub.2Me-AMD).sub.3.

[0034] FIG. 2 shows the thermogravimetric analysis (TGA) result of Tb(Et.sub.2nPr-AMD).sub.3.

[0035] FIG. 3 shows the differential scanning calorimetry (DSC) result of Tb(Et.sub.2nPr-AMD).sub.3.

[0036] FIG. 4 shows the TGA result of Dy(Et.sub.2nPr-AMD).sub.3.

[0037] FIG. 5 shows the DSC result of Dy(Et.sub.2nPr-AMD).sub.3.

[0038] FIG. 6 shows the TGA result of Er(Et.sub.2nPr-AMD).sub.3.

[0039] FIG. 7 shows the DSC result of Er(Et.sub.2nPr-AMD).sub.3.

[0040] FIG. 8 shows the TGA result of Yb(Et.sub.2nPr-AMD).sub.3.

[0041] FIG. 9 shows the 1H-NMR result of Lu(Et.sub.2nPr-AMD).sub.3.

[0042] FIG. 10 shows the TGA result of Lu(Et.sub.2nPr-AMD).sub.3.

[0043] FIG. 11 shows the DSC result of Lu(Et.sub.2nPr-AMD).sub.3.

MODE FOR INVENTION

[0044] Hereinafter, the present disclosure will be described in more detail. All terms or words used in this specification and the appended claims should not be construed as being limited to general and dictionary meanings, but will be interpreted based on the meanings and concepts corresponding to the technical ideas of the present disclosure, following the principle that any inventor is allowed to define the concepts of terms as appropriate to describe the disclosure thereof in the best mode.

[0045] A precursor for forming a lanthanide metal-containing thin film, according to the present disclosure, is characterized by including a compound of Chemical Formula 1 below.

##STR00002##

[0046] In Chemical Formula 1, Ln refers to a lanthanide metal, R.sub.1 and R.sub.3 are each independently a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 1 to 5 carbon atoms, and R.sub.2 is a hydrogen atom, or a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 1 to 8 carbon atoms.

[0047] The lanthanide metal refers to 15 elements ranging from the atomic numbers 57, lanthanum (La), to 71, lutetium (Lu), which 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).

[0048] In the amidinate ligand, R.sub.1 and R.sub.3 may be the same or different.

[0049] Additionally, R.sub.2 constituting the amidinate ligand in Chemical Formula 1 may be a hydrogen atom, or a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 1 to 8 carbon atoms. Preferably, R.sub.2 includes an n-alkyl group, such as an ethyl group, a propyl group, or a butyl group.

[0050] The precursor for forming the thin film can form various types of compounds with varying functional groups.

[0051] In one embodiment, R.sub.2 in Chemical Formula 1 may be a hydrogen atom, or a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 1 to 4 carbon atoms.

[0052] Additionally, R.sub.1 and R.sub.3 may each independently be a straight-chain, branched-chain, or cyclic alkyl or alkenyl group having 2 to 5 carbon atoms. Alternatively, R.sub.1 and R.sub.3 may be ethyl groups, and R.sub.2 may be an n-propyl group.

[0053] Additionally, R.sub.1 and R.sub.3 may each independently be a straight-chain alkyl or alkenyl group having 1 to 5 carbon atoms.

[0054] Additionally, in Chemical Formula 1, R.sub.2 may be a straight-chain alkyl or alkenyl group having 1 to 8 carbon atoms.

[0055] Additionally, in Chemical Formula 1, R.sub.1 and R.sub.3 may both be the same, and may be straight-chain, branched-chain, or cyclic alkyl or alkenyl groups having 1 to 5 carbon atoms.

[0056] Additionally, examples of the compound represented by Chemical Formula 1 constituting the precursor for forming the thin film, as described above, may include the following compounds: [0057] Ln(Me.sub.2,H-AMD).sub.3, Ln(Me.sub.2,Me-AMD).sub.3, Ln(Me.sub.2,Et-AMD).sub.3, Ln(Me.sub.2,nPr-AMD).sub.3, Ln(Me.sub.2,iPr-AMD).sub.3, Ln(Me.sub.2,nBu-AMD).sub.3, Ln(Me.sub.2,isoBu-AMD).sub.3, Ln(Me.sub.2,secBu-AMD).sub.3, Ln(Me.sub.2,tertBu-AMD).sub.3, Ln(Me.sub.2,n-pentyl-AMD).sub.3, Ln(Me.sub.2,sec-pentyl-AMD).sub.3, Ln(Me.sub.2,cyclopentyl-AMD).sub.3, Ln(Me.sub.2,n-hexyl-AMD).sub.3, Ln(Et,Me,H-AMD).sub.3, Ln(Et,Me,Me-AMD).sub.3, Ln(Et,Me,Et-AMD).sub.3, Ln(Et,Me,nPr-AMD).sub.3, Ln(Et,Me,iPr-AMD).sub.3, Ln(Et,Me,nBu-AMD).sub.3, Ln(Et,Me,isoBu-AMD).sub.3, Ln(Et,Me,secBu-AMD).sub.3, Ln(Et,Me,tertBu-AMD).sub.3, Ln(Et,Me,n-pentyl-AMD).sub.3, Ln(Et,Me,sec-pentyl-AMD).sub.3, Ln(Et,Me,cyclopentyl-AMD).sub.3, Ln(Et,Me,n-hexyl-AMD).sub.3, Ln(Et.sub.2,H-AMD).sub.3, Ln(Et.sub.2,Me-AMD).sub.3, Ln(Et.sub.2,Et-AMD).sub.3, Ln(Et.sub.2,nPr-AMD).sub.3, Ln(Et.sub.2,iPr-AMD).sub.3, Ln(Et.sub.2,nBu-AMD).sub.3, Ln(Et.sub.2,isoBu-AMD).sub.3, Ln(Et.sub.2,secBu-AMD).sub.3, Ln(Et.sub.2,tertBu-AMD).sub.3, Ln(Et.sub.2,n-pentyl-AMD).sub.3, Ln(Et.sub.2,sec-pentyl-AMD).sub.3, Ln(Et.sub.2,cyclopentyl-AMD).sub.3, Ln(Et.sub.2,n-hexyl-AMD).sub.3, Ln(Et,nPr,H-AMD).sub.3, Ln(Et,nPr,Me-AMD).sub.3, Ln(Et,nPr,Et-AMD).sub.3, Ln(Et,nPr,nPr-AMD).sub.3, Ln(Et,nPr,iPr-AMD).sub.3, Ln(Et,nPr,nBu-AMD).sub.3, Ln(Et,nPr,isoBu-AMD).sub.3, Ln(Et,nPr,secBu-AMD).sub.3, Ln(Et,nPr,tertBu-AMD).sub.3, Ln(Et,nPr,n-pentyl-AMD).sub.3, Ln(Et,nPr,sec-pentyl-AMD).sub.3, Ln(Et,nPr,cyclopentyl-AMD).sub.3, Ln(Et,nPr,n-hexyl-AMD).sub.3, Ln(nPr,Me,H-AMD).sub.3, Ln(nPr,Me,Me-AMD).sub.3, Ln(nPr,Me,Et-AMD).sub.3, Ln(nPr,Me,nPr-AMD).sub.3, Ln(nPr,Me,iPr-AMD).sub.3, Ln(nPr,Me,nBu-AMD).sub.3, Ln(nPr,Me,isoBu-AMD).sub.3, Ln(nPr,Me,secBu-AMD).sub.3, Ln(nPr,Me,tertBu-AMD).sub.3, Ln(nPr,Me,n-pentyl-AMD).sub.3, Ln(nPr,Me,sec-pentyl-AMD).sub.3, Ln(nPr,Me,cyclopentyl-AMD).sub.3, Ln(nPr,Me,n-hexyl-AMD).sub.3, Ln(nPr.sub.2,H-AMD).sub.3, Ln(nPr.sub.2,Me-AMD).sub.3, Ln(nPr.sub.2,Et-AMD).sub.3, Ln(nPr.sub.2,nPr-AMD).sub.3, Ln(nPr.sub.2,iPr-AMD).sub.3, Ln(nPr.sub.2,nBu-AMD).sub.3, Ln(nPr.sub.2,isoBu-AMD).sub.3, Ln(nPr.sub.2,secBu-AMD).sub.3, Ln(nPr.sub.2,tertBu-AMD).sub.3, Ln(nPr.sub.2,n-pentyl-AMD).sub.3, Ln(nPr.sub.2,sec-pentyl-AMD).sub.3, Ln(nPr.sub.2,cyclopentyl-AMD).sub.3, and Ln(nPr.sub.2,n-hexyl-AMD).sub.3.

[0058] The compound represented by Chemical Formula 1 is a precursor containing the amidinate ligand, in which the lanthanide metal serves as a central metal atom. This precursor has high thermal stability and volatility and may be in liquid form at room temperature. Therefore, the chemical properties of a desired precursor can be obtained by synthesizing the precursor containing the ligand.

[0059] Specifically, the precursor for forming the thin film may be liquid at room temperature.

[0060] Through such a chemical structure of the precursor for forming the thin film, a liquid precursor having high heat resistance and high volatility can be obtained, thereby enabling the formation of a high-quality thin film.

[0061] Additionally, the precursor for forming the thin film of the present disclosure may further include a solvent for dissolving or diluting the precursor compound, in consideration of conditions and efficiency of the thin-film formation process. As for the solvent, any one or a mixture of saturated or unsaturated hydrocarbons having 1 to 16 carbon atoms, ketones, ethers, glymes, esters, THF, and tertiary amines may be used. Examples of the saturated or unsaturated hydrocarbons having 1 to 16 carbon atoms may include toluene and heptane, octane, and examples of the tertiary amines may include dimethylethylamine.

[0062] In particular, depending on the chemical structure, the precursor compound for forming the thin film may be in a solid form at room temperature. In this case, the compound can be dissolved by involving the solvent. In other words, when involving the solvent, the solvent has a content enabling dissolution of the precursor compound, which is preferably included in an amount in the range of 1 to 99 wt % with respect to the total weight of the precursor for forming the thin film.

[0063] The precursors with or without the solvent are vaporizable and thus may be fed into a chamber in the form of precursor gas. Therefore, depending on the types of precursor compounds for forming the thin film, the precursor may be present as a liquid at room temperature and, when being easily vaporizable, the thin-film formation process may be performed even without involving additional solvents.

[0064] Additionally, the process of forming the lanthanide metal-containing thin film may be performed by any one of the following: an SOD process, an LTP process, a CVD process, a PECVD process, an HDPCVD process, an ALD process, or a PEALD process.

[0065] For example, when being applied, the HDPCVD process may be performed at high vacuum and high power compared to an atmospheric-pressure CVD (APCVD), low-pressure CVD (LPCVD), or PECVD process, thereby enabling the formation of a thin film that is structurally dense and exhibits excellent mechanical properties.

[0066] To this end, a method for forming a thin film, according to the present disclosure, includes a process of forming a thin film on a substrate using the above precursor for forming the thin film.

[0067] Specifically, the process of forming a lanthanide metal-containing thin film on the substrate may include the following processes: forming a precursor thin film through deposition of the precursor for forming the thin film onto the surface of the substrate, and reacting the precursor thin film with a reactant.

[0068] Additionally, for the deposition of the precursor, a process of vaporizing the precursor for forming the thin film so as to transfer the resulting vapor of the precursor into a chamber may be included.

[0069] Additionally, the process of forming the lanthanide metal-containing thin film on the substrate may include a process of feeding the precursor for forming the thin film onto the substrate and applying a plasma in the presence of the reactant, thereby forming a metal thin film, an oxide thin film, a nitride thin film, an oxynitride thin film, and the like.

[0070] The process of forming the thin film may be performed under an in-chamber pressure in the range of 1 to 1000 mTorr. Additionally, it is suitable that a source power for plasma formation in the chamber is in the range of 500 to 9,000 W, while a bias power is in the range of 0 to 5,000 W. Furthermore, the bias power may not be applied in some cases.

[0071] Additionally, the process of forming the thin film on the substrate may be performed at a temperature in the range of 150 C. to 500 C.

[0072] Additionally, when feeding the precursor for forming the thin film, a second metal precursor may be introduced, as needed, in order to further improve the electrical properties of a metal film to be ultimately formed, that is, to improve the capacitance or reduce the leakage current value. As for the second metal precursor, a metal precursor containing one or more metals (M) selected from silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta), and actinide (Ac) atoms may further be optionally fed. The second metal precursor may be an alkoxy-based compound or an alkylamide-based compound containing the metal described above. When the metal is Si, examples of the second metal precursor used may include SiH(N(CH.sub.3).sub.2).sub.3, Si(N(C.sub.2H.sub.5).sub.2).sub.4, Si(N(C.sub.2H.sub.5)(CH.sub.3)).sub.4, Si(N(CH.sub.3).sub.2).sub.4, Si(OC.sub.4H.sub.9).sub.4, Si(OC.sub.2H.sub.5).sub.4, Si(OCH.sub.3).sub.4, and Si(OC(CH.sub.3).sub.3).sub.4.

[0073] The feeding of the second metal precursor may be performed in the same manner as the feeding of the precursor for forming the thin film. Additionally, the second metal precursor may be fed onto the substrate for forming the thin film in combination with the precursor, or may be fed sequentially after the precursor is completely fed.

[0074] Before being fed into the reaction chamber, the precursor for forming the thin film and, optionally, the second metal precursor described above are preferably maintained at a temperature in the range of 50 C. to 250 C. and are more preferably maintained at a temperature in the range of 100 C. to 200 C., so as to make contact with the substrate for forming the thin film.

[0075] Additionally, after the step of feeding the precursor and before feeding the reactant, a purge process using an inert gas, such as argon (Ar), nitrogen (N.sub.2), or helium (He), in a reactor may be performed to help the precursor and, optionally, the second metal precursor move onto the substrate or allow for the internal pressure of the reactor suitable for deposition and also to remove impurities from the chamber to the outside. In this case, the purge process using the inert gas is preferably performed so that the internal pressure of the reactor is in the range of 1 to 5 Torr.

[0076] Additionally, as for the reactant, one or more of the following may be used: nitrogen (N.sub.2), ammonia (NH.sub.3), hydrazine (N.sub.2H.sub.4), nitrous oxide (N.sub.2O), oxygen (O.sub.2), water vapor (H.sub.2O), ozone (O.sub.3), hydrogen peroxide (H.sub.2O.sub.2), silane, hydrogen (H), and diborane (B.sub.2H.sub.6). When the thin-film formation process is performed in the presence of oxidizing gases such as water vapor, oxygen, and ozone, as described above, a magnesium oxide thin film may be formed. Alternatively, when the thin-film formation process is performed in the presence of reducing gases such as hydrogen, ammonia, hydrazine, and silane, a pure metal thin film or metal nitride thin film may be formed. Additionally, a metal oxynitride thin film may be formed by a mixture of the reactants.

[0077] Furthermore, a treatment process through heat treatment or light irradiation may be performed in addition to plasma treatment. This treatment process is configured to provide the heat energy required to deposit the precursor for forming the thin film, and may be performed by known methods. Preferably, to manufacture thin films having the desired physical state and composition at a sufficient growth rate, it is desirable that the above treatment process is performed so that the temperature of the substrate in the reactor is in the range of 100 C. to 1,000 C., preferably in the range of 250 C. to 400 C.

[0078] Additionally, even during the above treatment process, a purge process using an inert gas, such as argon (Ar), nitrogen (N.sub.2), or helium (He), in a reactor may be performed to help the reactant move onto the substrate or allow for the internal pressure of the reactor suitable for deposition and also to remove impurities or byproducts from the reactor to the outside, as described above.

[0079] The treatment process including the feeding of the precursor for forming the thin film, the feeding of the reactant, and the feeding of the inert gas, as described above, is defined as one cycle, and by repeatedly performing one or more cycles, a thin film can be formed.

[0080] Additionally, with the application of the thin-film formation process above, various semiconductor devices including such a thin film may be manufactured.

[0081] The following examples are to describe the effects of the present disclosure.

[Comparative Example 1] Synthesis of tris-(diisopropyl-methylamidinato)lanthanum [La(iPr.SUB.2.Me-AMD).SUB.3.]

[0082] To a 500 mL Schlenk flask, 20.0 g (0.0815 mol) of LaCl.sub.3 and 160 mL of THF were added, followed by stirring at room temperature for 4 hours. Subsequently, 80 mL of THF and 155.5 mL (0.2487 mol) of a MeLi-diethyl ether solution (1.6 M) were added to the 500 mL Schlenk flask and then cooled to 78 C., followed by slowly adding 30.86 g (0.2446 mol) of 1,3-diisopropylcarbodiimide dropwise and stirring at room temperature for 6 hours, thereby preparing Li-(iPr.sub.2Me-AMD). The prepared Li-(iPr.sub.2Me-AMD) solution was added dropwise to the flask containing 20.0 g (0.0815 mol) of LaCl.sub.3 at 0 C., followed by stirring at room temperature for 12 hours. The resulting mixture was filtered, followed by evaporation of the solvent and volatiles from the filtrate under vacuum. The unevaporated residues were then distilled at 260 C. and 150 mTorr, thus obtaining a light yellow solid. The yield was 25.1 g (54.7%).

[0083] The .sup.1H-NMR (AV400 MHz HD from Bruker) result shown in FIG. 1 confirmed that a lanthanide metal compound of Chemical Formula 1-1 below was synthesized.

##STR00003##

[Example 1] Synthesis of tris-(diethyl-n-propylamidinato)terbium [Tb(Et.SUB.2.nPr-AMD).SUB.3.]

[0084] To a 500 mL Schlenk flask, 10.0 g (0.0377 mol) of TbCl.sub.3 and 50 mL of THF were added, followed by stirring at room temperature for 4 hours. Subsequently, 50 mL of THF and 16.1 g (0.114 mol) of diethyl-n-propylamidinate were added to a 250 mL Schlenk flask and then cooled to 78 C., followed by slowly adding 47.5 mL (0.119 mol) of an n-BuLi-hexane solution (2.5 M) dropwise and stirring at room temperature for 2 hours, thereby preparing Li-(Et.sub.2nPr-AMD). The prepared Li-(Et.sub.2nPr-AMD) solution was added dropwise to the flask containing 10 g (0.0377 mol) of TbCl.sub.3 at 0 C., followed by stirring at room temperature for 6 hours. The resulting mixture was filtered, followed by evaporation of the solvent and volatiles from the filtrate under vacuum. The unevaporated residues were then distilled at 220 C. and 138 m Torr, thus obtaining a yellow liquid. The yield was 11.0 g (50.1%), and the resulting compound was identified as a lanthanide metal compound of Chemical Formula 1-2 below.

##STR00004##

[0085] During TGA measurement (SDT Q600 from TA Instruments) performed at a temperature ramp rate of 10 C./min in a nitrogen atmosphere at a flow rate of 200 mL/min, the yellow liquid had a residual mass of 1.18%, indicating that there were almost no residues left. This result was confirmed by the TGA result in FIG. 2, which shows the percentage of weight loss as a function of temperature.

[0086] Additionally, the yellow liquid sample was placed in a sealed container for DSC and maintained at 40 C. for 10 minutes. Subsequently, a decomposition peak was observed at 417 C. during DSC measurement (Discovery 25 from TA Instruments) performed at a temperature ramp rate of 10 C./min. This result was confirmed by the DSC result in FIG. 3, which shows the heat energy change as a function of temperature.

[Example 2] Synthesis of tris-(diethyl-n-propylamidinato)dysprosium [Dy(Et.SUB.2.nPr-AMD).SUB.3.]

[0087] To a 500 mL Schlenk flask, 10.0 g (0.0372 mol) of DyCl.sub.3 and 50 mL of THF were added, followed by stirring at room temperature for 4 hours. Subsequently, 50 mL of THF and 15.9 g (0.112 mol) of diethyl-n-propylamidinate were added to a 250 mL Schlenk flask and then cooled to 78 C., followed by slowly adding 46.9 mL (0.117 mol) of an n-BuLi-hexane solution (2.5 M) dropwise and stirring at room temperature for 2 hours, thereby preparing Li-(Et.sub.2nPr-AMD). The prepared Li-(Et.sub.2nPr-AMD) solution was added dropwise to the flask containing 10 g (0.0372 mol) of DyCl.sub.3 at 0 C., followed by stirring at room temperature for 6 hours. The resulting mixture was filtered, followed by evaporation of the solvent and volatiles from the filtrate under vacuum. The unevaporated residues were then distilled at 220 C. and 90 mTorr, thus obtaining a yellow liquid. The yield was 13.8 g (69%), and the resulting compound was identified as a lanthanide metal compound of Chemical Formula 1-3 below.

##STR00005##

[0088] During TGA measurement (SDT Q600 from TA Instruments) performed at a temperature ramp rate of 10 C./min in a nitrogen atmosphere at a flow rate of 200 mL/min, the yellow liquid had a residual mass of 1.59%, indicating that there were almost no residues left. This result was confirmed by the TGA result in FIG. 4, which shows the percentage of weight loss as a function of temperature.

[0089] Additionally, the yellow liquid sample was placed in a sealed container for DSC and maintained at 40 C. for 10 minutes. Subsequently, a decomposition peak was observed at 487 C. during DSC measurement (Discovery 25 from TA Instruments) performed at a temperature ramp rate of 10 C./min. This result was confirmed by the DSC result in FIG. 5, which shows the heat energy change as a function of temperature.

[Example 3] Synthesis of tris-(diethyl-n-propylamidinato)erbium [Er(Et.SUB.2.nPr-AMD).SUB.3.]

[0090] To a 500 mL Schlenk flask, 10.0 g (0.0365 mol) of ErCl.sub.3 and 50 mL of THF were added, followed by stirring at room temperature for 4 hours. Subsequently, 50 mL of THF and 15.6 g (0.110 mol) of diethyl-n-propylamidinate were added to a 250 mL Schlenk flask and then cooled to 78 C., followed by slowly adding 46.0 mL (0.115 mol) of an n-BuLi-hexane solution (2.5 M) dropwise and stirring at room temperature for 2 hours, thereby preparing Li-(Et.sub.2nPr-AMD). The prepared Li-(Et.sub.2nPr-AMD) solution was added dropwise to the flask containing 10 g (0.0365 mol) of ErCl.sub.3 at 0 C., followed by stirring at room temperature for 6 hours. The resulting mixture was filtered, followed by evaporation of the solvent and volatiles from the filtrate under vacuum. The unevaporated residues were then distilled at 220 C. and 80 mTorr, thus obtaining an orange liquid. The yield was 14 g (72%), and the resulting compound was identified as a lanthanide metal compound of Chemical Formula 1-4 below.

##STR00006##

[0091] During TGA measurement (SDT Q600 from TA Instruments) performed at a temperature ramp rate of 10 C./min in a nitrogen atmosphere at a flow rate of 200 mL/min, the orange liquid had a residual mass of 1.52%, indicating that there were almost no residues left. This result was confirmed by the TGA result in FIG. 6, which shows the percentage of weight loss as a function of temperature.

[0092] Additionally, the orange liquid sample was placed in a sealed container for DSC and maintained at 40 C. for 10 minutes. Subsequently, a decomposition peak was observed at 466 C. during DSC measurement (Discovery 25 from TA Instruments) performed at a temperature ramp rate of 10 C./min. This result was confirmed by the DSC result in FIG. 7, which shows the heat energy change as a function of temperature.

[0093] To further examine the viscosity of the orange liquid, this sample was placed in a measurement container of a rotational viscometer (LVD2T from Brookfield) for viscosity measurement at 25 C. using a low-viscosity spindle. The viscosity was found to be 77.1 cPs.

[Example 4] Synthesis of tris-(diethyl-n-propylamidinato)ytterbium [Yb(Et.SUB.2.nPr-AMD).SUB.3.]

[0094] Toa 500 mL Schlenk flask, 10.0 g (0.0358 mol) of YbCl.sub.3 and 50 mL of THF were added, followed by stirring at room temperature for 4 hours. Subsequently, 50 mL of THF and 15.3 g (0.107 mol) of diethyl-n-propylamidinate were added to a 250 mL Schlenk flask and then cooled to 78 C., followed by slowly adding 45.1 mL (0.113 mol) of an n-BuLi-hexane solution (2.5 M) dropwise and stirring at room temperature for 2 hours, thereby preparing Li-(Et.sub.2nPr-AMD). The prepared Li-(Et.sub.2nPr-AMD) solution was added dropwise to the flask containing 10 g (0.0358 mol) of YbCl.sub.3 at 0 C., followed by stirring at room temperature for 6 hours. The resulting mixture was filtered, followed by evaporation of the solvent and volatiles from the filtrate under vacuum. The unevaporated residues were then distilled at 220 C. and 68 mTorr, thus obtaining a yellow liquid. The yield was 14 g (70%), and the resulting compound was identified as a lanthanide metal compound of Chemical Formula 1-5 below.

##STR00007##

[0095] During TGA measurement (SDT Q600 from TA Instruments) performed at a temperature ramp rate of 10 C./min in a nitrogen atmosphere at a flow rate of 200 mL/min, the yellow liquid had a residual mass of 1.68%, indicating that there were almost no residues left. This result was confirmed by the TGA result in FIG. 8, which shows the percentage of weight loss as a function of temperature.

[0096] To further examine the viscosity of the yellow liquid, this sample was placed in a measurement container of a rotational viscometer (LVD2T from Brookfield) for viscosity measurement at 25 C. using a low-viscosity spindle. The viscosity was found to be 66.2 cPs.

[Example 5] Synthesis of tris-(diethyl-n-propylamidinato)lutetium [Lu(Et.SUB.2.nPr-AMD).SUB.3.]

[0097] To a 500 mL Schlenk flask, 10.0 g (0.0355 mol) of LuCl.sub.3 and 50 mL of THF were added, followed by stirring at room temperature for 4 hours. Subsequently, 50 mL of THF and 15.2 g (0.107 mol) of diethyl-n-propylamidinate were added to a 250 mL Schlenk flask and then cooled to 78 C., followed by slowly adding 44.8 mL (0.112 mol) of an n-BuLi-hexane solution (2.5 M) dropwise and stirring at room temperature for 2 hours, thereby preparing Li-(Et.sub.2nPr-AMD). The prepared Li-(Et.sub.2nPr-AMD) solution was added dropwise to the flask containing 10 g (0.0355 mol) of LuCl.sub.3 at 0 C., followed by stirring at room temperature for 6 hours. The resulting mixture was filtered, followed by evaporation of the solvent and volatiles from the filtrate under vacuum. The unevaporated residues were then distilled at 220 C. and 54 mTorr, thus obtaining an orange liquid. The yield was 16.2 g (75.8%).

[0098] The .sup.1H-NMR (AV400 MHz HD from Bruker) result of the above compound is as shown in FIG. 9, and the characteristic peaks observed at 0.88 (t, 9H), 1.30 (t, 18H), 1.51 (q, 6H), 2.21 (q, 6H), and 3.28 (q, 12H) confirm the synthesis of a lanthanide metal compound of Chemical Formula 1-6 below.

##STR00008##

[0099] During TGA measurement (SDT Q600 from TA Instruments) performed at a temperature ramp rate of 10 C./min in a nitrogen atmosphere at a flow rate of 200 mL/min, the orange liquid had a residual mass of 0.95%, indicating that there were almost no residues left. This result was confirmed by the TGA result in FIG. 10, which shows the percentage of weight loss as a function of temperature.

[0100] Additionally, the orange liquid sample was placed in a sealed container for DSC and maintained at 40 C. for 10 minutes. Subsequently, a decomposition peak was observed at 442 C. during DSC measurement (Discovery 25 from TA Instruments) performed at a temperature ramp rate of 10 C./min. This result was confirmed by the DSC result in FIG. 11, which shows the heat energy change as a function of temperature.

[0101] The present disclosure has been described hereinabove with reference to preferred embodiments, but is not limited to these embodiments. Various modifications and changes may be made by those skilled in the art to which the present disclosure belongs without departing from the idea of the present disclosure. Such modifications and changes should be construed as falling within the scope of the present disclosure and the appended claims.