Group 5 metal compound for thin film deposition and method of forming group 5 metal-containing thin film using same

Abstract

A group 5 metal compound according to an embodiment of the present disclosure is represented by any one of the following <Chemical Formula 1> and <Chemical Formula 2>: ##STR00001## In <Chemical Formula 1> and <Chemical Formula 2>, M is any one selected from group 5 metal elements, n is any one selected from an integer of 1 to 5, R.sub.1 is any one selected from a linear alkyl group having 3 to 6 carbon atoms and a branched alkyl group having 3 to 6 carbon atoms, and R.sub.2 and R.sub.3 are each independently any one selected from hydrogen, a linear alkyl group having 1 to 4 carbon atoms, and a branched alkyl group having 1 to 4 carbon atoms.

Claims

1. A group 5 metal compound represented by the following <Chemical Formula ##STR00006## wherein M is any one selected from the group 5 metal elements.

2. A precursor composition for depositing a group 5 metal-containing thin film, the precursor composition comprising the group 5 metal compound represented by the following <Chemical Formula 1>: ##STR00007## wherein M is any one selected from the group 5 metal elements.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and other aspects, features and other advantages of the present disclosure will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:

(2) FIG. 1 is a table showing calorie (differential scanning calorimetry) analysis results of ((η-C.sub.5H.sub.5)C.sub.5H.sub.9) (tBuN)Nb(OiPr).sub.2 according to Example 1, (η-C.sub.5H.sub.5) (tBuN)Nb(OiPr).sub.2 according to Example 2, and TBTDEN according to Comparative Example; and

(3) FIG. 2 is a graph showing thermogravimetric analysis (TGA) results of ((η-C.sub.5H.sub.5)C.sub.5H.sub.9)(tBuN)Nb(OiPr).sub.2 according to Example 1, (η-C.sub.5H.sub.5) (tBuN)Nb(OiPr).sub.2 according to Example 2, and TBTDEN according to Comparative Example.

DETAILED DESCRIPTION OF THE EMBODIMENT

(4) Hereinafter, preferred embodiments of the present disclosure will be described in more detail with reference to FIGS. 1 and 2. Embodiments of the present disclosure may be modified in various forms, and the scope of the present disclosure should not be construed as being limited to the embodiments described below. The present embodiments are provided to explain the present disclosure in more detail to a person having ordinary skill in the art to which the present disclosure pertains. Therefore, the shape of each element shown in the drawings may be exaggerated to emphasize a clearer explanation.

(5) In the entire specification of the present disclosure, the term “alkyl” or “an alkyl group” includes a linear or branched alkyl group having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, 1 to 3 carbon atoms, 3 to 8 carbon atoms, or 3 to 5 carbon atoms. For example, although the alkyl group may be selected from the group consisting of a methyl group, an ethyl group, an n-propyl group (.sup.nPr), an iso-propyl group (.sup.iPr), an n-butyl group (.sup.nBu), a tert-butyl group (.sup.tBu), an iso-butyl group (.sup.iBu), a sec-butyl group (.sup.sBu), an n-pentyl group, a tert-pentyl group, an iso-pentyl group, a sec-pentyl group, a neopentyl group, a 3-pentyl group, a hexyl group, an isohexyl group, a heptyl group, a 4,4-dimethylpentyl group, an octyl group, a 2,2,4-trimethylpentyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and isomers thereof, it is not limited thereto.

(6) A group 5 metal compound according to an embodiment of the present disclosure may be represented by any one of the following Chemical Formula 1 and Chemical Formula 2:

(7) ##STR00003##

(8) In <Chemical Formula 1> and <Chemical Formula 2>, M is any one selected from group 5 metal elements, n is any one selected from an integer of 1 to 5, R.sub.1 is any one selected from a linear alkyl group having 3 to 6 carbon atoms and a branched alkyl group having 3 to 6 carbon atoms, and R.sub.2 and R.sub.3 are each independently any one selected from hydrogen, a linear alkyl group having 1 to 4 carbon atoms, and a branched alkyl group having 1 to 4 carbon atoms.

(9) More specifically, M may be any one selected from the group consisting of vanadium (V), niobium (Nb), and tantalum (Ta). In addition, R.sub.1 may be any one selected from the group consisting of an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, a tert-pentyl group, an iso-pentyl group, a sec-pentyl group, a neopentyl group, and a 3-pentyl group. Moreover, R.sub.2 and R.sub.3 may be each independently any one selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group, and R.sub.2 and R.sub.3 may have the same structure.

(10) More specifically, the group 5 metal compound represented by Chemical Formula 1 may be a group 5 metal compound represented by the following Chemical Formula 3:

(11) ##STR00004##

(12) In Chemical Formula 3, M is any one selected from group 5 metal elements, and is the same as described in Chemical Formula 1.

(13) In addition, the group 5 metal compound represented by Chemical Formula 2 may be a group 5 metal compound represented by the following Chemical Formula 4:

(14) ##STR00005##

(15) A group 5 metal compound according to an embodiment of the present disclosure has a structure in which a group 5 metal and cyclopentadiene are directly connected. A group 5 metal compound according to an embodiment of the present disclosure has excellent thermal stability since the group 5 metal compound can maintain a more structurally stable state by enabling electrons to be more easily supplied to the metal from cyclopentadiene. Accordingly, when forming a thin film using a group 5 metal compound according to an embodiment of the present disclosure, it is possible to reduce the amount of residue generated in the deposition process. In addition, since it is easy to apply the group 5 metal compound to a liquid process, it may be used in the atomic layer deposition (ALD) process.

(16) Furthermore, in a group 5 metal compound according to an embodiment of the present disclosure, a group 5 metal forms a double bond with one nitrogen atom, and forms a single bond with two oxygen atoms respectively. A bonding energy between a group 5 metal, e.g., niobium (Nb) and an oxygen atom (0) is greater than that between niobium (Nb) and a nitrogen atom (N). Therefore, compared with a compound in which a group 5 metal and three nitrogen atoms are connected by allowing the group 5 metal to form a double bond with one nitrogen atom and form a single bond with each of two nitrogen atoms, a group 5 metal compound according to an embodiment of the present disclosure has more excellent thermal stability.

(17) Hereinafter, a group 5 metal compound according to the present disclosure will be described in more detail through the following examples. However, this is only presented to help to understand the present disclosure, and the present disclosure is not limited to the following examples.

Example 1: Preparation of ((η-C.SUB.5.H.SUB.5.)C.SUB.5.H.SUB.9.) (tBuN)Nb(OiPr).SUB.2

(18) After injecting 20 g (0.0453 mol, 1 equivalent) of bis(diethylamido) (tert-butylimido) (cyclopentylcyclopentadiene)niobium ((η-C.sub.5H.sub.5)C.sub.5H.sub.9) (tBuN)Nb(NEt.sub.2).sub.2 and 150 mL of hexane (n-hexane) into a flame-dried 500 mL Schlenk flask, the injected materials were stirred at room temperature. After adding dropwise 5.99 g (0.0997 mol, 2.2 equivalents) of isopropyl alcohol (C.sub.3H.sub.7OH) to the flask at −20° C. or lower, a reaction solution was stirred at room temperature for 12 hours. 18.73 g (yield 98%) of a light-yellow liquid compound represented by ((η-C.sub.5H.sub.5)C.sub.5H.sub.9) (tBuN)Nb(OiPr).sub.2 was obtained by removing a solvent from the reaction solution under reduced pressure and distilling the solvent-removed reaction solution under reduced pressure.

Example 2: Preparation of (η-C.SUB.5.H.SUB.5.) (tBuN)Nb(OiPr).SUB.2

(19) After injecting 11 g (0.029 mol, 1 equivalent) of bis(diethylamido) (tert-butylimido) (cyclopentadiene)niobium ((η-C.sub.5H.sub.5) (tBuN)Nb(NEt.sub.2).sub.2 and 150 mL of hexane (n-hexane) into a flame-dried 500 mL Schlenk flask, the injected materials were stirred at room temperature. After adding dropwise 3.8 g (0.063 mol, 2.2 equivalents) of isopropyl alcohol (C.sub.3H.sub.7OH) to the flask at −20° C. or lower, a reaction solution was stirred at room temperature for 12 hours. 9 g (yield 90%) of a light-yellow liquid compound represented by ((η-C.sub.5H.sub.5) (tBuN)Nb(OiPr).sub.2 was obtained by removing a solvent from the reaction solution under reduced pressure and distilling the solvent-removed reaction solution under reduced pressure.

Experimental Example: Thermal Analysis

(20) In order to find out thermal properties of (t-butylimido)tris(diethylamino)niobium(V)) (TBTDEN) according to Comparative Example, ((η-C.sub.5H.sub.5)C.sub.5H.sub.9)(tBuN)Nb(OiPr).sub.2 according to Example 1, and (η-C.sub.5H.sub.5) (tBuN)Nb(OiPr).sub.2 according to Example 2 under similar conditions, differential scanning calorimetry (DSC) analysis and thermogravimetic analysis (TGA) were performed. A thermogravimetric device was stored in a nitrogen glove box in which the moisture and oxygen contents were kept below 1 ppm. The thermogravimetric analysis was performed by putting 15 mg of a sample into a crucible. Thereafter, the sample was heated from 35° C. to 350° C. with a 10° C./min temperature gradient. The mass loss was monitored as a function of crucible temperature. The decomposition temperatures (Td) of Comparative Example, Example 1, and Example 2 according to the DSC analysis are shown in FIG. 1. In addition, the graph results according to the TGA are shown in FIG. 2. Referring to FIG. 1 and FIG. 2, it can be confirmed that ((η-C.sub.5H.sub.5)C.sub.5H.sub.9)(tBuN)Nb(OiPr).sub.2 prepared according to Example 1 and (η-C.sub.5H.sub.5) (tBuN)Nb(OiPr).sub.2 prepared according to Example 2 are more thermally stable than TBTDEN prepared according to Comparative Example. It can be seen from this that ((η-C.sub.5H.sub.5)C.sub.5H.sub.9) (tBuN)Nb(OiPr).sub.2 according to Example 1 and (η-C.sub.5H.sub.5) (tBuN)Nb(OiPr).sub.2 according to Example 2 are more effectively used as vapor phase precursors.

(21) Hereinafter, a method of forming a group 5 metal-containing thin film according to an embodiment of the present disclosure will be described.

(22) A method of forming a group 5 metal-containing thin film according to an embodiment of the present disclosure deposits a thin film on a substrate through a deposition process using a group 5 metal compound according to an embodiment of the present disclosure as a precursor.

(23) The deposition process may be included of an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process, for example, a metal organic chemical vapor deposition (MOCVD) process. The deposition process may be carried out at 50 to 700° C.

(24) First, a group 5 metal compound represented by any one of Chemical Formula 1 and Chemical Formula 2 is transferred onto a substrate. For example, although the group 5 metal compound may be supplied onto the substrate by a bubbling method, a vapor phase mass flow controller method, a direct gas injection (DGI) method, a direct liquid injection (DLI) method, a liquid transfer method in which the liquid is dissolved in an organic solvent and transferred, etc., the present disclosure is not limited thereto.

(25) More specifically, the group 5 metal compound is mixed with a carrier gas or dilution gas containing one or more selected from the group consisting of argon (Ar), nitrogen (N.sub.2), helium (He), and hydrogen (H.sub.2) so that a mixture of the group 5 metal compound and the carrier gas or dilution gas is transferred onto the substrate by the bubbling method or the DGI method.

(26) Meanwhile, the deposition process may include a step of supplying one or more reaction gases selected from the group consisting of water vapor (H.sub.2O), oxygen (O.sub.2), ozone (O.sub.3), and hydrogen peroxide (H.sub.2O.sub.2) when forming a group 5 metal-containing thin film. In addition, the deposition process may include a step of supplying one or more reaction gases selected from the group consisting of ammonia (NH.sub.3), hydrazine (N.sub.2H.sub.4), nitrous oxide (N.sub.2O), and nitrogen (N.sub.2) when forming a group 5 metal-containing thin film. Through this, a metal-containing thin film formed on the substrate may be a group 5 metal oxide film or a group 5 metal nitride film.

(27) Hereinabove, the present disclosure has been described in detail through examples, but other types of examples that are different from them are also possible. Therefore, the technical spirit and scope of the claims set forth below are not limited to the examples.