KR102570721B1 - Novel Multi Component Organometallic Compounds, Preparation method thereof, and Method for deposition of thin film using the same - Google Patents

Abstract

The present invention relates to an organometallic compound, a method for preparing the same, and a method for manufacturing a thin film using the same, and more particularly, in manufacturing a thin film through chemical vapor deposition or a solution process, thermal stability and volatility are improved, It relates to an organometallic compound that can easily produce a high-quality ternary metal thin film, ternary metal oxide thin film or ternary metal chalcogen thin film at low temperature, a method for preparing the same, and a method for manufacturing a thin film using the same.

Description

Novel Multi Component Organometallic Compounds, Preparation method thereof, and Method for deposition of thin film using the same}

The present invention relates to a novel multi-component organometallic compound, a method for preparing the same, and a method for forming a thin film using the same, and more particularly, in manufacturing a thin film through a solution process, thermal stability is improved and high quality It relates to a novel multi-component organometallic compound capable of producing a ternary metal thin film, a ternary metal oxide thin film, or a ternary metal chalcogen thin film, a method for preparing the same, and a method for manufacturing a thin film using the same.

Since two-dimensional semiconductors containing transition metal chalcogen compounds such as MoS ₂ and WS ₂ have only two-dimensional interactions with constituent atoms, transport of carriers is very different from that of conventional thin films or bulks, resulting in high mobility. , high speed and low power are expected.

In particular, as a semiconductor device with high mobility and low power consumption, transparent and flexible characteristics can be a great advantage because the thickness of the semiconductor layer is within several nm. When the material is manufactured with a single layer or a thickness of several layers, it exhibits direct transition characteristics and is excellent in photoreactivity, so its utilization in photoelectric devices is expected at the same time.

It is known that MoS ₂ , a typical TMDC (Transition Metal Di-Chalcogenide) material, has indirect transition characteristics when present in a thick film or bulk state and has a band gap of 1.2 to 1.3 eV. On the other hand, when thinned to about a single layer to about five layers, it exhibits direct transition characteristics. It is known that the band gap is 1.8~1.9 eV for a single layer and gradually decreases to the bulk band gap as the number of layers increases.

In addition, WS ₂ as the TMDC (Transition Metal Di-Chalcogenide) material can be grown into a thin film using CVD. For example, after depositing a tungsten (W) thin film on a silicon oxide (SiO ₂ ) substrate, it is placed in a Chemical Vapor Deposition (CVD) system and heated to supply sulfur (S) gas to grow WS ₂ WS ₂ can be transferred onto an ITO/Glass substrate, and this technology can be usefully used in the development of semiconductors or solar cells because it is easy to use for large areas.

In addition, the MoS ₂ and WS ₂ can be used as a catalyst in reactions such as hydrocracking and hydrogen evolution reaction, or as a sensor, so various applications are expected.

In this way, chemical vapor deposition (CVD) or atomic layer deposition (ALD) or a solution process is used to form a thin film containing a transition metal chalcogen. In the case of producing a homogeneous tungsten or molybdenum thin film, a metal precursor Since the deposition degree and deposition control characteristics are determined according to the characteristics of the metal precursor, it is necessary to develop a metal precursor having excellent characteristics.

In addition, in recent years, in manufacturing transition metal chalcogen materials (thin films) such as MoS ₂ and WS ₂ , the chalcogen element (S) is not simultaneously or sequentially added separately from the metal precursor, and a metal source is included. Attempts have been made to form a transition metal chalcogen thin film by introducing a chalcogen element into the precursor itself.

In this case, when manufacturing a transition metal chalcogen thin film such as MoS ₂ , WS ₂ , a separate chalcogen element (S) is not additionally added in the thin film manufacturing process, and the chalcogen element is introduced as a ligand in the metal precursor together. It may have the advantage of being able to form a more simple and uniform thin film.

As a conventional technology related to a precursor for forming such a thin film, Korean Patent Publication No. 10-2007-0073636 studies a method for preparing a tungsten or molybdenum precursor containing a diamine ligand. No. 10-2015-0084757 discloses a molybdenum precursor comprising a cyclopentadienyl group and an imido group as ligands, but they cannot directly form a WS ₂ or MoS ₂ thin film, and also thermally In terms of stability, chemical reactivity, and volatility, further improvement is needed.

On the other hand, two-dimensional MoS ₂ doped with a transition metal and In order to manufacture a WS ₂ thin film, there is a need to go through various stages of electrochemical processes, so there is a need to develop a precursor that can solve this problem at once.

Therefore, thermal stability is improved, and a metal thin film, a metal oxide thin film, or a metal chalcogen thin film can be easily manufactured at a low temperature, and in addition, a novel multi-component molybdenum as a precursor for a solution process containing a transition metal component. Alternatively, the need for development of a tungsten organometallic compound and a manufacturing process of a thin film having more improved physical properties using the same is continuously required.

Korean Patent Publication No. 10-2007-0073636 (published on July 10, 2007) Korean Patent Publication No. 10-2015-0084757 (published on July 22, 2015)

The first technical problem to be achieved by the present invention is to provide a novel organometallic compound as a precursor capable of producing a ternary metal thin film or a ternary metal chalcogen thin film doped with a transition metal and having improved thermal stability.

In addition, the second technical problem to be achieved by the present invention is to provide a novel method for preparing the organometallic compound.

In addition, a third technical problem to be achieved by the present invention is to provide a method for manufacturing a ternary metal thin film, a ternary metal oxide thin film, or a ternary metal chalcogen thin film using the organometallic compound as a precursor.

In order to achieve the above technical objects, the present invention provides an organometallic compound represented by the following [Formula A] or [Formula B].

[Formula A]

[Formula B]

In the above formula A and formula B,

M is any one metal element selected from Ni, Co, Fe, Ru, Rh, Pd, Os, Ir, Pt, Ti, Al, Cu, Mg, V, B, Cr, Zr and Zn,

The E ₁ and E ₂ are each the same or different and independently of each other, sulfur (S) or selenium (Se).

A ₁ and A ₂ are each the same or different and independently of each other, H ⁺ , Li ⁺ . Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , NH ₄ ⁺ , N ⁺ (R ₁ R ₂ R ₃ R ₄ ), a monovalent imidazole cation having 1 to 10 carbon atoms, a monovalent pyridine cation having 1 to 10 carbon atoms, And P ⁺ (R ₁ R ₂ R ₃ R ₄ ) Any one monovalent cation selected from,

B is Ca ²⁺ , Mg ²⁺ , (R ₁ R ₂ R ₃ )N ⁺ -RN ⁺ (R ₄ R ₅ R ₆ ), (R ₁ R ₂ R ₃ )P ⁺ -RP ⁺ (R ₄ R Any one 2 selected from ₅ R ₆ ), Mg ²⁺ (NR ₁ R ₂ R ₃ ) ₆ , Ni ²⁺ (NR ₁ R ₂ R ₃ ) ₆ and Co ²⁺ (NR ₁ R ₂ R ₃ ) ₆ is a cation,

Wherein R ₁ to R ₆ are each the same or different and independently of each other, hydrogen, heavy hydrogen, a substituted or unsubstituted C1-C20 linear, branched or cyclic alkyl group; A substituted or unsubstituted C1-C20 cycloalkyl group; A substituted or unsubstituted C6-C20 aryl group; and a substituted or unsubstituted C2-C20 heteroaryl group; any one selected from

Wherein R is an unsubstituted C1-C20 linear, branched or cyclic alkylene group; A substituted or unsubstituted C1-C20 cycloalkylene group; A substituted or unsubstituted C6-C20 arylene group; and a substituted or unsubstituted C2-C20 heteroarylene group; any one selected from

'Substitution' in 'substituted or unsubstituted' in Formulas A and B is deuterium, a cyano group, a halogen group, a nitro group, a C1-C10 linear or branched alkyl group, a C1-C10 halogenated alkyl group , C3-C12 cycloalkyl group, C6-C12 means substituted with one or more substituents selected from aryl groups.

In addition, the present invention relates to a metal halide compound represented by compound M; molybdenum chalcogenides represented by the following compound C1; and tungsten chalcogenide represented by compound C2; to prepare an organometallic compound represented by formula A or formula B, characterized in that for preparing an organometallic compound represented by formula A or formula B using each as a reactant. provides a way

[Compound M] MX ₁ X ₂

[Compound C1] [Compound C2]

AMo(E ₁ ) ₄ ^2- A'W(E ₂ ) ₄ ^2-

[Formula A]

[Formula B]

In the compound M,

said X ₁ and X ₂ are each the same or different and each independently represents any one halogen element selected from F, Cl, Br, and I;

In the above formula C1 and formula C2,

A is a divalent cation corresponding to Mo(E ₁ ) ₄ ^2- or two same or different monovalent cations,

A' is W(E ₂ ) ₄ ^2- Means a divalent cation corresponding to or two identical or different monovalent cations,

In Formula A, Formula B, Formula C1 and Formula C2,

The E ₁ and E ₂ are each the same or different and independently of each other, sulfur (S) or selenium (Se).

M, A _{1 ,} A ₂ and B in the compound M, formula A and formula B are the same as defined above, respectively.

The organometallic compound represented by [Formula A] or [Formula B] of the present invention can be used as a precursor for forming a metal thin film, a metal oxide thin film, or a metal chalcogen thin film for a solution process, in particular, a metal knife. It can be used as a precursor for forming a cogen thin film.

In addition, since the organometallic compound represented by [Formula A] or [Formula B] exhibits improved thermal stability, it is possible to form a large-area or uniform thin film, and also, sulfur (S) and / or contains a component of selenium (Se), so when forming a transition metal chalcogen thin film, a transition metal chalcogen through a one step annealing process using a single precursor without adding a separate chalcogen component It has the advantage of being able to easily form a thin film.

In addition, the metal chalcogen thin film made of the organometallic compound according to the present invention is prepared using a precursor containing a cationic leaving group instead of a conventionally used metal halide precursor, so that during the manufacturing process of the metal chalcogen thin film, halogen gas, etc. It can provide the advantage of no contamination and corrosion of the thin film manufacturing apparatus due to the occurrence of.

1 is prepared according to Preparation Example 1 of the present invention This is the X-ray crystal structure of the compound (Ph ₄ P) ₂ [Ni(MoS ₄ )(WS ₄ )].
Figure 2 is prepared according to Preparation Example 1 of the present invention (Ph ₄ P) ₂ [Ni(MoS ₄ )(WS ₄ )] This is a thermogravimetric analysis (TGA) result for the compound.
Figure 3 is prepared according to Preparation Example 1 of the present invention (Ph ₄ P) ₂ [Ni(MoS ₄ )(WS ₄ )] This is a photograph of a film prepared by spin-coating the compound.

Hereinafter, the present invention will be described in more detail. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is one well known and commonly used in the art.

Throughout the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

The present inventors have made efforts to achieve the above technical problems and to develop a precursor for producing a ternary metal thin film having excellent properties, and as a result, a metal corresponding to the central metal (M) in the compound represented by Formula A or Formula B By reacting molybdenum chalcogenide represented by compound C1 and tungsten chalcogenide represented by compound C2 below with halide (MX ₁ X ₂ ), respectively,

[Compound M] MX ₁ X ₂

[Compound C1] [Compound C2]

AMo(E ₁ ) ₄ ^2- A'W(E ₂ ) ₄ ^2-

', which is a divalent anion moiety in the structures of Formula A and Formula B It was possible to prepare the part, and the organic metal represented by the formula A or formula B according to the present invention through a cation exchange reaction by reacting the composite complex obtained after the reaction with a salt containing A1 and A2 or a salt containing B compound could be prepared.

The organometallic compound represented by Formula A or Formula B obtained according to the present invention can be used as a precursor for preparing a ternary metal chalcogen thin film using a solution process.

That is, the organometallic compound represented by Formula A or Formula B is a ternary organometallic compound in which molybdenum (Mo) and central metal (M) are bridged with two sulfur (S) atoms or selenium (Se) atoms, respectively. Forms a covalent bond, and the central metal (M) and tungsten (W) form a bridged covalent bond with two sulfur (S) atoms or selenium (Se) atoms, respectively, and molybdenum (Mo) and tungsten at the ends As a structure in which (W) forms a bond with two sulfur (S) atoms or / and selenium (Se) atoms, respectively, a divalent anion is formed as a whole, and as a corresponding cation, in Formula A, A1 and A2 are overall Represents a divalent cation, and in Formula B, B represents a divalent cation.

Accordingly, through the structure of Formula A or Formula B, it has excellent chemical-thermal stability in a solution process, and in addition, sulfur (S) or / and selenium (Se), which are chalcogen elements, in the precursor itself containing a transition metal By introducing, the present invention was completed by confirming that it can be utilized as a useful precursor for forming a transition metal chalcogen thin film.

That is, the organometallic compound represented by Formula A or Formula B in the present invention contains sulfur (S) or/and selenium (Se) as a chalcogen component in the precursor itself including a transition metal source, At the time of manufacturing the ternary transition metal chalcogen thin film, there is an advantage in that a ternary transition metal chalcogen thin film can be manufactured even if a separate chalcogen element (S or Se) is not added simultaneously or sequentially in addition to the transition metal component, and the transition metal is doped. In order to manufacture a two-dimensional MoS ₂ /WS ₂ thin film, there is a hassle of having to go through various stages of electrochemical processes, but the organometallic compound according to the present invention has the advantage of solving these problems at once.

In addition, the metal chalcogen thin film made of the organometallic compound according to the present invention has a structure in which divalent transition metal ions such as Pd ²⁺ , Ni ²⁺ , Co ²⁺ are doped on the surface of the two-dimensional transition metal chalcogen thin film structure. can form, and when these divalent transition metals are included in the two-dimensional structure (absorption), they have the advantage of further increasing the activity when used as catalysts in reactions such as hydrocracking and Hydrogen evolution reaction. It is expected to show excellent activity in the hydrogen generating reaction electrode as it is used as an active point where the reduction reaction proceeds by adsorption.

Hereinafter, the present invention will be described in more detail.

The present invention provides an organometallic compound represented by the following [Formula A] or [Formula B].

[Formula A]

[Formula B]

In the above formula A and formula B,

M is any one metal selected from Ni, Co, Fe, Ru, Rh, Pd, Os, Ir, Pt, Ti, Al, Cu, Mg, V, B, Cr, Zr, and Zn;

The E ₁ and E ₂ are each the same or different and independently of each other, sulfur (S) or selenium (Se).

A ₁ and A ₂ are each the same or different and independently of each other, H ⁺ , Li ⁺ . Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , NH ₄ ⁺ , N ⁺ (R ₁ R ₂ R ₃ R ₄ ), a monovalent imidazole cation having 1 to 10 carbon atoms, a monovalent pyridine cation having 1 to 10 carbon atoms, And P ⁺ (R ₁ R ₂ R ₃ R ₄ ) Any one monovalent cation selected from,

B is Ca ²⁺ , Mg ²⁺ , (R ₁ R ₂ R ₃ )N ⁺ -RN ⁺ (R ₄ R ₅ R ₆ ), (R ₁ R ₂ R ₃ )P ⁺ -RP ⁺ (R ₄ R Any one 2 selected from ₅ R ₆ ), Mg ²⁺ (NR ₁ R ₂ R ₃ ) ₆ , Ni ²⁺ (NR ₁ R ₂ R ₃ ) ₆ and Co ²⁺ (NR ₁ R ₂ R ₃ ) ₆ is a cation,

Wherein R ₁ to R ₆ are each the same or different and independently of each other, hydrogen, heavy hydrogen, a substituted or unsubstituted C1-C20 linear, branched or cyclic alkyl group; A substituted or unsubstituted C1-C20 cycloalkyl group; A substituted or unsubstituted C6-C20 aryl group; and a substituted or unsubstituted C2-C20 heteroaryl group; any one selected from

Wherein R is an unsubstituted C1-C20 linear, branched or cyclic alkylene group; A substituted or unsubstituted C1-C20 cycloalkylene group; A substituted or unsubstituted C6-C20 arylene group; and a substituted or unsubstituted C2-C20 heteroarylene group; any one selected from

'Substitution' in 'substituted or unsubstituted' in [Formula A] and Formula B is deuterium, a cyano group, a halogen group, a nitro group, a C1-C10 linear or branched alkyl group, a C3-C12 cycloalkyl group , It means that it is substituted with one or more substituents selected from C6-C12 aryl groups.

Here, in the organometallic compound represented by [Formula A] or [Formula B], molybdenum (Mo) and the central metal (M) are two sulfur (S) atoms or selenium (Se) atoms in the ternary organometallic compound, respectively. It forms a bridged covalent bond with an atom, and the center metal (M) and tungsten (W) form a bridged covalent bond with two sulfur (S) atoms or selenium (Se) atoms, respectively, and molybdenum (terminal) Mo) and tungsten (W) form a bond with two sulfur (S) atoms or / and selenium (Se) atoms, respectively, and have an anion structure that forms a divalent anion as a whole, and as a corresponding cation component , H ⁺ , Li ⁺ . Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , NH ₄ ⁺ , N ⁺ (R ₁ R ₂ R ₃ R ₄ ), a monovalent imidazole cation having 1 to 10 carbon atoms, a monovalent pyridine cation having 1 to 10 carbon atoms, and contains two monovalent cations selected from P ⁺ (R ₁ R ₂ R ₃ R ₄ ), or Ca ²⁺ , Mg ²⁺ , (R ₁ R ₂ R ₃ )N ⁺ -RN ⁺ ( R ₄ R ₅ R ₆ ), (R ₁ R ₂ R ₃ )P ⁺ -RP ⁺ (R ₄ R ₅ R ₆ ), Mg ²⁺ (NR ₁ R ₂ R ₃ ) ₆ , Ni ²⁺ (NR ₁ R It includes one divalent cation selected from ₂ R ₃ ) ₆ and Co ²⁺ (NR ₁ R ₂ R ₃ ) ₆ .

Through this, the organometallic compound represented by [Formula A] or [Formula B] according to the present invention can exhibit thermal stability, and thus can be used in a solution process, a ternary metal thin film, a ternary metal oxide thin film, or a ternary system. It can be applied as a precursor for metal chalcogen thin films.

In addition to this, as previously described Likewise, sulfur (S) and/or selenium (Se), which are chalcogen elements, are included in the molecule of a precursor compound including a transition metal source in combination with molybdenum, tungsten, or a central metal (M) atom, thereby forming a ternary transition metal chalcogen When used as a precursor for thin film production, the sulfur (S) atom or/and selenium (Se) atom may have an additional advantage of being used as a chalcogen (S) source.

Meanwhile, in the organometallic compound represented by [Formula A] according to the present invention, A ₁ and A ₂ , which are monovalent cations, are preferably the same or different and independently of each other, P ⁺ (R ₁ R ₂ R ₃ R ₄ ), and in the organometallic compound including P ⁺ (R ₁ R ₂ R ₃ R ₄ ), during the thin film manufacturing process, the alkyl chain or aryl chain in the compound is a metal decal It is expected to stabilize the layered structure of the metal dichalcogen thin film by serving as a capping agent according to the planar structure of the aryl chain or the chain structure of the alkyl chain between the layered structures of the metal dichalcogen thin film.

In addition, in the organometallic compound represented by [Formula A] according to the present invention, specific examples of A ₁ and A ₂ , which are monovalent cations, are the same or different and independently of each other, H ⁺ , tetraphenylphosponium, It may be any one selected from CTA (cetyltrimethylammonium), tetraethylammonium, 1-ethyl-3-methylimidazolinium, and pyridinium.

Further, in the organometallic compound represented by [Formula A] according to the present invention, when A ₁ and A ₂ are the same or different and independently of each other, P ⁺ (R ₁ R ₂ R ₃ R ₄ ) In the above, R ₁ to R ₄ are each the same or different and independently of each other, a substituted or unsubstituted C6-C20 aryl group; and a substituted or unsubstituted C2-C20 heteroaryl group; It may be any one selected from, and in this case, the R ₁ to R ₄ may use the same substituent as each other.

In addition, the central metal (M) used in the organometallic compound represented by [Formula A] or [Formula B] according to the present invention is preferably Ni, Co, Fe, Ru, Rh, Pd, Os, Ir and Any one selected from Pt may be used, and more preferably, any one metal element selected from Ni, Co, Fe, and Pd may be used.

In addition, the present invention provides a method for manufacturing a metal thin film, a metal oxide thin film or a metal chalcogen thin film using the organometallic compound represented by the above formula A or formula B as a metal precursor, and a thin film obtained by the above manufacturing method. This may be performed by a solution process method capable of forming a thin film by dissolving and coating the precursor in a solvent.

According to the solution process method according to the present invention, the organometallic compound represented by Formula A or Formula B may be preferably used as a precursor for preparing a metal dichalcogen compound.

That is, the present invention provides a composition for a solution process comprising the organometallic compound represented by Formula A or Formula B.

In this case, the composition for the solution process may additionally include an organic solvent, and suitable organic solvents include toluene, tetrahydrofuran, hexane, cyclohexane, acetonitrile, dimethylformamide, Dimethylsulfoxide (DMSO), Isopropyl Alcohol (IPA) and the like, but is not limited thereto, preferably acetonitrile, dimethylformamide, Dimethyl sulfoxide (DMSO) and isopropyl alcohol (IPA) can be used.

In addition, the content of the organometallic compound represented by Formula A or Formula B in the solution process composition based on the total composition content may be 1 to 20 wt%, preferably in the range of 1.5 to 15 wt%. It may be, more preferably 2 to 10 wt%. If the content of the organometallic compound is less than 1 wt%, the production rate of the thin film according to the process time is too slow, resulting in a very low productivity. Therefore, it is difficult to obtain a uniform metal thin film, metal oxide thin film or metal chalcogen thin film.

On the other hand, the present invention is a halogenated metal compound represented by compound M; molybdenum chalcogenides represented by the following compound C1; and a tungsten chalcogenide represented by Compound C2; each of which is used as a reactant to provide a method for producing an organometallic compound represented by Formula A or Formula B.

[Compound M] MX ₁ X ₂

[Compound C1] [Compound C2]

AMo(E ₁ ) ₄ ^2- A'W(E ₂ ) ₄ ^2-

[Formula A]

[Formula B]

In the compound M,

X ₁ and X ₂ are each the same or different and each independently represent any one halogen element selected from F, Cl, Br, and I;

In the above formula C1 and formula C2,

A is a divalent cation corresponding to Mo(E ₁ ) ₄ ^2- or two same or different monovalent cations,

A' is W(E ₂ ) ₄ ^2- Means a divalent cation corresponding to or two identical or different monovalent cations,

In Formula A, Formula B, Formula C1 and Formula C2,

The E ₁ and E ₂ are each the same or different and independently of each other, sulfur (S) or selenium (Se).

In the above compound M, formula A and formula B,

M is any one metal element selected from Ni, Co, Fe, Ru, Rh, Pd, Os, Ir, Pt, Ti, Al, Cu, Mg, V, B, Cr, Zr and Zn,

A ₁ and A ₂ are each the same or different and independently of each other, H ⁺ , Li ⁺ . Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , NH ₄ ⁺ , N ⁺ (R ₁ R ₂ R ₃ R ₄ ), a monovalent imidazole cation having 1 to 10 carbon atoms, a monovalent pyridine cation having 1 to 10 carbon atoms, and Any one monovalent cation selected from P ⁺ (R ₁ R ₂ R ₃ R ₄ );

B is Ca ²⁺ , Mg ²⁺ , (R ₁ R ₂ R ₃ )N ⁺ -RN ⁺ (R ₄ R ₅ R ₆ ), (R ₁ R ₂ R ₃ )P ⁺ -RP ⁺ (R ₄ R Any one 2 selected from ₅ R ₆ ), Mg ²⁺ (NR ₁ R ₂ R ₃ ) ₆ , Ni ²⁺ (NR ₁ R ₂ R ₃ ) ₆ and Co ²⁺ (NR ₁ R ₂ R ₃ ) ₆ is a cation,

Wherein R ₁ to R ₆ are each the same or different and independently of each other, hydrogen, heavy hydrogen, a substituted or unsubstituted C1-C20 linear, branched or cyclic alkyl group; A substituted or unsubstituted C1-C20 cycloalkyl group; A substituted or unsubstituted C6-C20 aryl group; and a substituted or unsubstituted C2-C20 heteroaryl group; any one selected from

Wherein R is an unsubstituted C1-C20 linear, branched or cyclic alkylene group; A substituted or unsubstituted C1-C20 cycloalkylene group; A substituted or unsubstituted C6-C20 arylene group; and a substituted or unsubstituted C2-C20 heteroarylene group; any one selected from

'Substitution' in 'substituted or unsubstituted' in Formulas A and B is deuterium, a cyano group, a halogen group, a nitro group, a C1-C10 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C6 -It means that it is substituted with one or more substituents selected from aryl groups of C12.

Here, A and A' in Formula C1 and Formula C2 are Mo(E ₁ ) ₄ ^2- or W(E ₂ ) ₄ ^2- Corresponds to a divalent cation corresponding to or two identical or different monovalent cations, where Mo(E ₁ ) ₄ ^2- or W(E ₂ ) ₄ ^2- Types of divalent cations corresponding to are Ca ²⁺ , Mg ²⁺ , (R ₁ R ₂ R ₃ )N ⁺ -RN ⁺ (R ₄ R ₅ R ₆ ), (R ₁ R ₂ R ₃ )P ⁺ - RP ⁺ (R ₄ R ₅ R ₆ ), Mg ²⁺ (NR ₁ R ₂ R ₃ ) ₆ , Ni ²⁺ (NR ₁ R ₂ R ₃ ) ₆ and Co ²⁺ (NR ₁ R ₂ R ₃ ) ₆ etc. And, in this case, the R ₁ to R ₆ are the same as defined above.

Also Mo(E ₁ ) ₄ ^2- or Examples of the monovalent cation corresponding to W(E ₂ ) ₄ ^2- include H ⁺ and Li ⁺ . Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , NH ₄ ⁺ , N ⁺ (R ₁ R ₂ R ₃ R ₄ ), a monovalent imidazole cation having 1 to 10 carbon atoms, a monovalent pyridine cation having 1 to 10 carbon atoms, and and P ⁺ (R ₁ R ₂ R ₃ R ₄ ). In this case, R ₁ to R ₄ are the same as defined above.

In the method for preparing the organometallic compound represented by Formula A or Formula B according to the present invention, a metal halide compound represented by Compound M; and a molybdenum chalcogenide represented by Compound C1; And tungsten chalcogenide represented by compound C2; obtained after the reaction of, A compound represented by Formula A or Formula B may be obtained by reacting the complex complex including the moiety with a salt containing A1 and A2 or a salt containing B to cause a cation exchange reaction.

That is, the metal halide compound represented by the compound M; molybdenum chalcogenide represented by the compound C1; And a tungsten chalcogenide represented by compound C2; each used as a reactant, but as a cation component capable of inducing a stable chemical structure by forming an ionic bond with an anion in the obtained ternary metal composite complex, H ⁺ , Li ⁺ . Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , NH ₄ ⁺ , N ⁺ (R ₁ R ₂ R ₃ R ₄ ), a monovalent imidazole cation having 1 to 10 carbon atoms, a monovalent pyridine cation having 1 to 10 carbon atoms, and In the case of using any one monovalent cation selected from P ⁺ (R ₁ R ₂ R ₃ R ₄ ) (using a salt containing A1 and A2), the compound represented by Formula A is prepared, and the cation As components, Ca ²⁺ , Mg ²⁺ , (R ₁ R ₂ R ₃ )N ⁺ -RN ⁺ (R ₄ R ₅ R ₆ ), (R ₁ R ₂ R ₃ )P ⁺ -RP ⁺ (R ₄ R Any one 2 selected from ₅ R ₆ ), Mg ²⁺ (NR ₁ R ₂ R ₃ ) ₆ , Ni ²⁺ (NR ₁ R ₂ R ₃ ) ₆ and Co ²⁺ (NR ₁ R ₂ R ₃ ) ₆ In the case of using a valent cation (using a salt containing B), the compound represented by Formula B may be prepared.

Here, in the method for producing compound A according to the present invention, it is a salt containing A1 and A2 as a mediator for cation exchange, preferably a monovalent compound represented by P ⁺ (R ₁ R ₂ R ₃ R ₄ ) A halogenated salt containing a cation may be used, and in this case, the R ₁ to R ₄ are the same or different and independently of each other, a substituted or unsubstituted C6-C20 aryl group; and a substituted or unsubstituted C2-C20 heteroaryl group; It may be any one selected from, and preferably, the R ₁ to R ₄ may be the same as each other.

In addition, in the method for preparing compound B according to the present invention, as a salt containing B as a mediator for cation exchange, preferably (R ₁ R ₂ R ₃ )P ⁺ -RP ⁺ (R ₄ R ₅ R ₆ ) may be used a halogenated salt containing a divalent cation represented by R ₁ to R ₆ are each the same or different and independently of each other, a substituted or unsubstituted C6-C20 aryl group; and a substituted or unsubstituted C2-C20 heteroaryl group; It may be any one selected from, wherein preferably the R ₁ to R ₆ may be the same as each other, wherein R is an unsubstituted C1-C20 linear, branched or cyclic alkylene group; and a substituted or unsubstituted C1-C20 linear, branched or cyclic halogenated alkylene group; A substituted or unsubstituted C1-C20 cycloalkylene group; A substituted or unsubstituted C6-C20 arylene group; and a substituted or unsubstituted C2-C20 heteroarylene group; It may be any one selected from among.

In addition, in the method for preparing compound A or compound B according to the present invention, the metal (M) in compound M is preferably selected from Ni, Co, Fe, Ru, Rh, Pd, Os, Ir and Pt Any one metal element, more preferably any one metal element selected from Ni, Co, Fe, and Pd.

Here, in preparing the organometallic compound represented by Formula A or Formula B, when an organic solvent is used, suitable organic solvents include toluene, tetrahydrofuran, hexane, cyclohexane, acetonitrile, dimethylformamide , dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA), and the like, but are not limited thereto, preferably acetonitrile, dimethylformamide, dimethyl sulfoxide (DMSO), and isopropyl alcohol (IPA). can be used

The reaction may preferably be carried out in the organic solvent at a temperature range of 0 to 100 ° C, preferably 10 to 40 ° C for 12 to 24 hours, through which the reaction is represented by Formula A or Formula B compounds can be formed.

In addition, in order to separate the product from by-products or unreacted products generated during the reaction, sublimation, distillation, extraction, column chromatography, recrystallization, etc. are used to separate the high-purity novel organometallic compound. can be obtained.

The organometallic compound represented by Formula A or Formula B of high purity thus obtained may be solid or liquid at room temperature, is thermally stable, and can be well dissolved in organic solvents, so that it can be used in a solution process.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for explaining the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

manufacturing example 1. (Ph ₄ P) ₂ [(MoS ₄ )Ni(WS ₄ )] synthesis of

(Ph4P)2[(MoS4)Ni(WS4)]

(NH ₄ ) ₂ MoS ₄ (1 mmol, 0.26 g) was dissolved in distilled water in a 100 ml Schlenk flask and stirred at low temperature. A solution of NiCl ₂ ㅇ6H ₂ O (1.1 mmol, 0.28 g) and Ph ₄ PCl (2 mmol, 0.65 g) in distilled water was added thereto, followed by stirring for 5 minutes. Then, a solution of (NH ₄ ) ₂ WS ₄ (1 mmol, 0.35 g) in distilled water was added, stirred for 10 minutes, and filtered to obtain a dark brown solid compound. The compound was dried under reduced pressure for 18 hours and recrystallized from acetonitrile and diethylether to obtain a reddish-brown solid compound.

EA: Anal. Calcd (Found) for C ₄₈ H ₄₀ MoWNiP ₂ S ₈ : C, 45.26 (46.15); H, 3.17 (3.21); S, 20.14 (16.59).

EDS (atomic % ratio): Ni 1; Mo 0.93; W 1.12; S 6.42; P 1.98.

Preparation Example 2. (Ph ₄ P) ₂ [(MoS ₄ )Co(WS ₄ )] synthesis of

(Ph4P)2[(MoS4)Co(WS4)]

(NH ₄ ) ₂ MoS ₄ (1 mmol, 0.26 g) was dissolved in distilled water in a 100ml Schlenk flask and stirred at low temperature. After adding a solution of CoCl ₂ ㅇ6H ₂ O (1 mmol, 0.24 g) and Ph ₄ PCl (2 mmol, 0.65 g) in distilled water, the mixture was stirred for 5 minutes. Then, a solution of (NH ₄ ) ₂ WS ₄ (1 mmol, 0.35 g) in distilled water was added, stirred for 10 minutes, and filtered to obtain a dark green solid compound. After drying the compound under reduced pressure for 18 hours, it was recrystallized from DMF and diethylether to obtain a reddish-brown solid compound.

EA: Anal. Calcd (Found) for C ₄₈ H ₄₀ MoWCoP ₂ S ₈ : C, 45.25 (45.0); H, 3.16 (3.02); S, 20.13 (13.82).

EDS (atomic % ratio): Co 1; Mo 0.93; W 0.98; S 7.03; P2.05.

Preparation Example 3. (Ph ₄ P) ₂ [(MoS ₄ )Fe(WS ₄ )] synthesis of

(Ph ₄ P) ₂ [(MoS ₄ )Fe(WS ₄ )]

(NH ₄ ) ₂ MoS ₄ (1 mmol, 0.26 g) was dissolved in distilled water in a 100ml Schlenk flask and stirred at low temperature. After adding a solution of FeCl ₂ ㅇ4H ₂ O (1 mmol, 0.198 g) and Ph ₄ PCl (2 mmol, 0.65 g) in distilled water, the mixture was stirred for 5 minutes. Then, a solution of (NH ₄ ) ₂ WS ₄ (1 mmol, 0.35 g) in distilled water was added, stirred for 10 minutes, and filtered to obtain a solid compound. After drying the compound under reduced pressure for 18 hours, it was recrystallized from DMF and diethylether to obtain a solid compound.

Preparation Example 4. (Ph ₄ P) ₂ [(MoS ₄ )Pd(WSe ₄ )] synthesis of

(Ph ₄ P) ₂ [(MoS ₄ )Pd(WSe ₄ )]

(Ph ₄ P) ₂ WSe ₄ (0.1 mmol, 0.09 g) was dissolved in DMF in a 50 ml Schlenk flask and stirred. After adding a solution of PdCl ₂ (CNC ₆ H ₅ ) (0.1 mmol, 0.038 g) and Et ₄ NCl (0.2 mmol, 0.033 g) in DMF, the mixture was stirred for 5 minutes. Then, a solution of (Ph ₄ P) ₂ MoS ₄ (1 mmol, 0.35 g) in DMF was added and stirred for 18 hours. The filter was added dropwise to diethyl ether, and a dark red solid was precipitated at 0 ^o C for 18 hours. After filtering, it was washed with methanol to obtain a red solid compound.

EA: Anal. Calcd (Found) for C ₄₈ H ₄₀ MoP ₂ PdS ₄ Se ₄ W: C, 17.62 (16.65); H, 3.70 (3.73); S, 11.76 (13.19); N, 2.57 (3.43)

EDS (atomic % ratio): Pd 1; Mo 0.87; W 1.1; S 4.03; SE 4.87; P 1.82.

Preparation Example 5. (Et ₄ N) ₂ [(MoS ₄ )Pd(WSe ₄ )] synthesis of

(Et ₄ N) ₂ [(MoS ₄ )Pd(WSe ₄ )]

(NH ₄ ) ₂ MoS ₄ (0.5 mmol, 0.13 g) was dissolved in DMF in a 50 ml Schlenk flask and stirred. After adding a solution of PdCl ₂ (CNC ₆ H ₅ ) (0.5 mmol, 0.19 g) in DMF, the mixture was stirred for 5 minutes. Then, a solution of (Et ₄ N) ₂ WSe ₄ (0.5 mmol, 0.478 g) in DMF was added and stirred for 18 hours. The filter was added dropwise to diethyl ether, and a dark red solid was precipitated at 0 ^o C for 18 hours. After filtering, it was washed with methanol to obtain a red solid compound.

EA: Anal. Calcd (Found) for C ₄₈ H ₄₀ MoWCoP ₂ S ₈ : C, 45.25 (45.0); H, 3.16 (3.02); S, 20.13 (13.82).

EDS (atomic % ratio): Co 1; Mo 0.93; W 0.98; S 7.03; P2.05.

Preparation Example 6. (imidazolinium) ₂ [(MoS ₄ )Pd(WSe ₄ )] synthesis of

(imidazolinium) ₂ [(MoS ₄ )Pd(WSe ₄ )]

In a 50ml Schlenk flask, (NH ₄ ) ₂ MoS ₄ (0.2mmol, 0.056g) was dissolved in DMF and stirred. A solution of PdCl ₂ (CNC ₆ H ₅ ) ₂ (0.2 mmol, 0.077 g) in DMF was added thereto, followed by stirring for 10 minutes. Then, a solution of (imidazolinium) ₂ WSe ₄ (0.2mmol, 1.44g) in DMF was added, stirred for 18 hours, and filtered. A black solid compound was obtained by recrystallization from diethylether.

EA: Anal. Calcd (Found) for C ₁₂ H ₂₂ MoN ₄ PdS ₄ Se ₄ W: C, 13.69 (13.66); H, 2.11 (2.13); S, 12.18 (13.09); N, 5.32 (5.18).

EDS (atomic % ratio): Pd 1; Mo 0.74; W 1.55; S 3.48; SE 4.95.

Preparation Example 7. (Ph ₄ P) ₂ [(MoS ₄ )Pd(WS ₄ )] synthesis of

(Ph ₄ P) ₂ [(MoS ₄ )Pd(WS ₄ )]

(NH ₄ ) ₂ MoS ₄ (1 mmol, 0.26 g) was dissolved in DMF in a 100 ml Schlenk flask and stirred. After adding a solution of PdCl ₂ (CNC ₆ H ₅ ) ₂ (1 mmol, 0.24 g) and Ph ₄ PCl (2 mmol, 0.65 g) in DMF, the mixture was stirred for 10 minutes. Then, a solution of (NH ₄ ) ₂ WS ₄ (1 mmol, 0.35 g) in DMF was added, stirred for 18 hours, and filtered. A red solid compound was obtained by recrystallization from diethylether.

EA: Anal. Calcd (Found) for C ₄₈ H ₄₀ MoWPdP ₂ S ₈ : C, 43.63 (43.46); H, 3.05 (3.25); S, 19.41 (18.28).

Example 1. Crystal structure analysis of the compound according to Preparation Example 1

In order to confirm the crystal structure of the organometallic compound ((Ph ₄ P) ₂ [(MoS ₄ )Ni(WS ₄ )]) prepared in Preparation Example 1, a SMART APEX II X-ray Diffractometer was used to determine the X-ray structure. was confirmed, and the crystal structure is shown in FIG.

Example 2. Analysis of thermal properties of the compound according to Preparation Example 1

In order to measure the thermal stability, volatility and decomposition temperature of the organometallic compound ((Ph ₄ P) ₂ [(MoS ₄ )Ni(WS ₄ )]) synthesized according to Preparation Example 1, thermogravimetric analysis (thermogravimetric analysis, TGA) method was used. In the TGA method, while heating the product to 900 °C at a rate of 10 °C/min, argon gas was injected at a pressure of 1.5 bar/min, and the results of the thermal decomposition experiment are shown in FIG. 2 .

According to the thermal characteristic analysis result according to FIG. 2, the final residual amount of the precursor compound according to Preparation Example 1 was observed to be 35.43%, and according to the TGA analysis result, the organometallic compound represented by [Formula A] of the present invention is It can be seen that it has good properties for forming a metal thin film, a metal oxide thin film or a metal chalcogen thin film.

Example 3. Spin coating of Preparation Example 1

The organometallic compound obtained according to Preparation Example 1 was dissolved in dimethylformamide to prepare a 5 wt% solution, which was then spin-coated on a SiO ₂ (300 nm)/Si(001) substrate UV-treated for 600 seconds. Spin coating was carried out at 0 rpm for 30 seconds and at 1000 rpm/2000 rpm for 20 seconds, then thin films were synthesized by evaporating dimethyl formamide at 100 ° C., and the uniformity of the formed thin films was measured with an optical microscope, which is shown in FIG. 3.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It falls within the scope of the right of invention.

Claims (12)

An organometallic compound represented by the following [Formula A] or [Formula B].
[Formula A]

[Formula B]

In the above formula A and formula B,
M is any one metal element selected from Ni, Co, Fe, Ru, Rh, Pd, Os, Ir, Pt, Ti, Al, Cu, Mg, V, B, Cr, Zr and Zn,
The E ₁ and E ₂ are each the same or different and independently of each other, sulfur (S) or selenium (Se).
A ₁ and A ₂ are each the same or different and independently of each other, H ⁺ , Li ⁺ . Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , NH ₄ ⁺ , N ⁺ (R ₁ R ₂ R ₃ R ₄ ), a monovalent imidazole cation having 1 to 10 carbon atoms, a monovalent pyridine cation having 1 to 10 carbon atoms, and Any one monovalent cation selected from P ⁺ (R ₁ R ₂ R ₃ R ₄ );
B is Ca ²⁺ , Mg ²⁺ , (R ₁ R ₂ R ₃ )N ⁺ -RN ⁺ (R ₄ R ₅ R ₆ ), (R ₁ R ₂ R ₃ )P ⁺ -RP ⁺ (R ₄ R Any one 2 selected from ₅ R ₆ ), Mg ²⁺ (NR ₁ R ₂ R ₃ ) ₆ , Ni ²⁺ (NR ₁ R ₂ R ₃ ) ₆ and Co ²⁺ (NR ₁ R ₂ R ₃ ) ₆ is a cation,
Wherein R ₁ to R ₆ are each the same or different and independently of each other, hydrogen, heavy hydrogen, a substituted or unsubstituted C1-C20 linear, branched or cyclic alkyl group; A substituted or unsubstituted C1-C20 cycloalkyl group; A substituted or unsubstituted C6-C20 aryl group; and a substituted or unsubstituted C2-C20 heteroaryl group; any one selected from
Wherein R is an unsubstituted C1-C20 linear, branched or cyclic alkylene group; A substituted or unsubstituted C1-C20 cycloalkylene group; A substituted or unsubstituted C6-C20 arylene group; and a substituted or unsubstituted C2-C20 heteroarylene group; any one selected from
'Substitution' in 'substituted or unsubstituted' in Formulas A and B is deuterium, a cyano group, a halogen group, a nitro group, a C1-C10 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C6 -It means that it is substituted with one or more substituents selected from aryl groups of C12.
According to claim 1,
Wherein A ₁ and A ₂ are each the same or different and independently of each other, P ⁺ (R ₁ R ₂ R ₃ R ₄ ) An organometallic compound, characterized in that.
According to claim 2,
Wherein R ₁ to R ₄ are the same or different and independently of each other, a substituted or unsubstituted C6-C20 aryl group; and a substituted or unsubstituted C2-C20 heteroaryl group; An organometallic compound, characterized in that any one selected from.
According to claim 3,
The R ₁ to R ₄ are organometallic compounds, characterized in that the same as each other.
According to claim 1,
Wherein M is an organometallic compound, characterized in that any one metal element selected from Ni, Co, Fe, Ru, Rh, Pd, Os, Ir and Pt.
A method for producing a metal chalcogen thin film by using any one organometallic compound selected from claims 1 to 5 as a metal precursor.
According to claim 6,
The method for producing a metal chalcogen thin film, characterized in that the process for producing the metal chalcogen thin film is performed by a solution process.
According to claim 7,
The method for producing a metal chalcogen thin film, characterized in that the metal chalcogen thin film comprises a metal dichalcogen compound.
A composition for a solution process comprising any one organometallic compound selected from claims 1 to 5.
According to claim 9,
The composition for a solution process, characterized in that the composition additionally comprises an organic solvent.
a metal halide compound represented by the following compound M; molybdenum chalcogenides represented by the following compound C1; and tungsten chalcogenide represented by compound C2; a method for producing an organometallic compound represented by formula A or formula B, characterized in that for producing an organometallic compound represented by formula A or formula B using each of the reactants. in
a metal halide compound represented by the compound M; and a molybdenum chalcogenide represented by the compound C1; and a tungsten chalcogenide represented by compound C2; a complex complex obtained after the reaction of a salt containing A ₁ and A ₂ ; Or a salt containing B; by reacting with a cation exchange reaction, the compound represented by the above formula A or formula B is obtained, characterized in that the organometallic represented by formula A or formula B of claim 1 Method for preparing the compound.
[Compound M] MX ₁ X ₂
[Compound C1] [Compound C2]
AMo(E ₁ ) ₄ ^2- A'W(E ₂ ) ₄ ^2-
[Formula A]

[Formula B]

In the compound M,
said X ₁ and X ₂ are each the same or different and each independently represents any one halogen element selected from F, Cl, Br, and I;
In the above formula C1 and formula C2,
A is a divalent cation corresponding to Mo(E ₁ ) ₄ ^2- or two identical or different monovalent cations,
A' is W(E ₂ ) ₄ ^2- Means a divalent cation corresponding to or two identical or different monovalent cations,
In Formula A, Formula B, Formula C1 and Formula C2,
The E ₁ and E ₂ are each the same or different and independently of each other, sulfur (S) or selenium (Se).
M, A _{1 ,} A ₂ and B in the compound M, formula A and formula B are each the same as defined in claim 1 above. delete