KR102231296B1 - A organic-metal precirsor compound and othin film prepared by using the same - Google Patents

Abstract

The organometallic precursor compound of the present invention and a method for producing an organometallic thin film using the same satisfy high volatility, excellent chemical and thermal stability, and have a significantly improved thin film deposition rate even at low temperatures. In addition, by providing an organometallic precursor compound that can be used to form a dielectric thin film in a semiconductor device, it is possible to prepare an organometallic and/or metal-containing thin film with improved characteristics deterioration due to by-products.

Description

Organometallic precursor compound and thin film prepared using the same {A ORGANIC-METAL PRECIRSOR COMPOUND AND OTHIN FILM PREPARED BY USING THE SAME}

The present invention relates to an organometallic precursor compound and an organometallic-containing thin film prepared using the same, and more particularly, an organometallic precursor compound that satisfies excellent chemical and thermal stability and facilitates thin film deposition even at low temperatures, and uses the same. It relates to a thin film including an organometallic deposition layer or a metal deposition layer prepared by doing so.

Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD) are thin films for semiconductor devices because they can achieve conformal thin films (metals, oxides, nitrides, etc.) through fine tuning of parameters during the process. It has been applied as a technique for deposition. Since thin film growth is mainly controlled by a chemical reaction of a metal-organic compound (precursor), it is important to develop an optimal precursor by predicting its properties and reaction process. Therefore, the development of efficient precursors for obtaining specific properties according to a specific type of thin film has been continued.

Precursors are molecules for CVD and ALD processes, and some of their intrinsic properties must be considered before using them. First, a liquid form and/or sufficient vapor pressure is required to easily transport the gaseous precursor from the containing vessel into the reaction chamber. Second, long-term thermal stability is required under storage and transport conditions, and thermal stability in gas phase is also required to prevent impurities from entering the thin film. Third, strong reactivity to a reactive gas such as ammonia or oxygen is required to easily convert the precursor to the required thin film on the sample substrate. Another important requirement that must be considered for the precursor during the precursor design stage is the removal of impurities derived from the ligand from the thin film during the deposition process.

Tungsten is used in a variety of applications useful in the fabrication of nano-devices. Deposition of pure tungsten can be used to fill the holes ("contact holes") that make junctions in the transistor source and drain, or to fill the vias between successive layers of metal. This method is known as the "tungsten plug" process. The _{use of WF 6} can diversify the use of tungsten due to the good properties of the deposited thin film. However, it is necessary to provide an adhesion/barrier layer, such as Ti/TiN, to protect Si under the penetration by fluorine, or to ensure adhesion of tungsten to silicon dioxide.

Tungsten-silicide can be used on top of the polysilicon gate to increase the conductivity of its gate line and thus increase the transistor speed. This method is widely used in DRAM manufacturing. The gate at this time is a word line for the circuit. WF ₆ and SiH ₄ can be used, but dichlorosilane (SiCl ₂ H ₂ ) is more commonly used as the silicon source, as it allows for higher deposition temperatures, resulting in lower fluorine concentrations in the deposited thin film. .

Tungsten nitride (WNx) is considered a good barrier to copper diffusion in microelectronic circuits. WNx can also be used for thin-film capacitors and electrodes for field-effect transistors.

WF ₆ can be used for deposition of pure tungsten thin films in CVD mode by using _{H 2} at high temperature because of the oxidation state of +6 of W, which is both liquid and highly volatile. In addition, WF ₆ can be used in a CVD mode in combination with silane to prepare a tungsten silicide thin film at a low temperature. However, WF ₆ is limited either by the high thermal budget required for the deposition of pure tungsten thin films, or by fluorine, which contributes to the etching of the underlying silicon surface.

It can be used for deposition of pure tungsten or tungsten nitride thin films in CVD mode because of the zero oxidation state of W in W(CO) _6. However, due to the high toxicity of this material, it has been limited to mass production.

Although W(CO) ₂ (1,3-butadiene) ₂ can be used in CVD mode, a deposition of a tungsten carbide thin film is formed.

However, in the biscyclopentadienyl tungsten precursor having the formula W(RCp) ₂ H ₂ , the +6 oxidation state of W can be used in the CVD mode for the deposition of pure tungsten, but a high deposition temperature is required, resulting in carbon contamination. do.

US 7,560,581B2 discloses the use of a bis-alkylimido bis-dialkylamino tungsten precursor to prepare tungsten nitride in ALD mode with or without copper barrier diffusion applications.

Apart from the aforementioned tungsten precursor, several diazabutadiene-based molecules have been developed. Diazabutadiene (DAD) ligands are diimine ligands that can be used under different oxidation states.

U.S. Patent 7,754,908 to Reuter et al. discloses the use of a bis-alkylimido diazabutadiene tungsten precursor for the production of tungsten-containing films. However, the use of an alkylimido group has a disadvantage in that carbon can be introduced in the resulting thin film. Tungsten molecules may contain several types of ligands that are not homologous ligands. Therefore, their synthesis is carried out in several stages, and the complexity and difficulty of the synthesis result in an increase in cost in the end.

Winter's WO2012/027357 discloses a method of forming a thin film on a substrate comprising contacting a surface with a precursor compound having a transition metal and at least one alkyl-1,3-diazabutadiene ligand. .

That is, when depositing a tungsten-containing thin film (pure tungsten, tungsten nitride, or tungsten silicide) in CVD or ALD mode, a high C, O, or F content in the thin film may be a problem. Therefore, in order to prepare a pure tungsten-containing thin film with few impurities, a tungsten precursor compound having high volatility and thermal stability, satisfies appropriate reactivity in the deposition process, and is easy to deposit even at low temperatures is required.

US Patent Publication No. US 2006-0125099 A1 (published date 2006.06.15.)

The present invention was devised to solve the above-described problems, and the problem to be solved by the present invention is an organometallic precursor compound that satisfies high volatility, excellent chemical and thermal stability, and facilitates deposition of a thin film even at low temperatures, and using the same. It is an object to provide a thin film including the prepared organometallic deposition layer or metal deposition layer.

The present invention provides an organometallic precursor compound represented by the following Formula 1 in order to solve the above-described problems.

[Formula 1]

이다.In Formula 1, M is a tungsten atom (W), a chromium atom (Cr) or a molybdenum atom (Mo), R ₁ is a C _2-10 alkylene group or a heteroalkylene group, and R ₂ is a C _1-5 An alkyl group or a heteroalkyl group, R ₃ and R ₄ are each independently a C _1-10 alkyl group, and X is a nitrogen atom (N), a number atom (P), an arsenic atom (As) or

to be.

According to a preferred embodiment of the present invention, X may be a nitrogen atom.

According to another preferred embodiment of the present invention, R ₁ may be a C _2-5 alkylene group.

According to another preferred embodiment of the present invention, R ₂ is a C _{1 to 3} alkyl group, and R ₃ and R ₄ may each independently be a C _{1 to 5} alkyl group.

In addition, the present invention provides an organometallic precursor compound represented by the following formula (2).

[Formula 2]

In Formula 2, M is a tungsten atom (W), a chromium atom (Cr) or a molybdenum atom (Mo), R ₁ ′ is an alkylene group or heteroalkylene group _{of C 1 to 4 , and R 2} is C _{1 to 5} Is an alkyl group or a heteroalkyl group, and R ₃ and R ₄ are each independently a C _1-10 alkyl group.

According to a preferred embodiment of the present invention, R ₁ ′ is a C _{1 to 2} alkyl group or a heteroalkyl group, R ₂ is a C _{1 to 3} alkyl group, and R ₃ and R ₄ are each independently C _{1 to 5} It may be an alkyl group of.

In addition, the present invention provides an organometallic precursor compound represented by the following formula (3).

[Formula 3]

In Formula 3, M is a tungsten atom (W), a chromium atom (Cr) or a molybdenum atom (Mo), R ₂ is an alkyl group of _{C 1 to 3 , and R 3} and R ₄ are each independently C _{1 to 5} It is an alkyl group of.

According to a preferred embodiment of the present invention, the organometallic precursor compound represented by Formula 3 may be represented by Formula 4 below.

[Formula 4]

In Formula 4, M is a tungsten atom (W), a chromium atom (Cr), or a molybdenum atom (Mo), and R ₃ and R ₄ are each independently a C _3-5 alkyl group.

In addition, the present invention provides an organometallic precursor compound, characterized in that represented by the following formula (5).

[Formula 5]

In Formula 5, M is a tungsten atom (W), a chromium atom (Cr), or a molybdenum atom (Mo).

In addition, the present invention provides an organometallic precursor compound, wherein any one of the organometallic precursor compounds is for manufacturing an organometallic-containing thin film for semiconductors.

Further, the present invention provides an organometallic deposition layer or a thin film including a metal deposition layer prepared by including any one of the organometallic precursor compounds as a precursor.

Hereinafter, terms used in the present specification will be briefly described.

The term “alkyl” refers to an aliphatic hydrocarbon group. The alkyl moiety may be a “saturated alkyl” group, which means that no alkene or alkyne moiety is included. The alkyl moiety may be an "unsaturated alkyl" moiety, which means that at least one alkene or alkyne moiety is included. Whether saturated or unsaturated alkyl, the alkyl moiety can be branched, straight or cyclic. In addition, alkyl includes both "substituted or unsubstituted alkyl".

The term “substituted or unsubstituted” means that the substituent is substituted and unsubstituted, unless otherwise specified, and when substituted, the substituent is alkyl, acyl, cycloalkyl (dicyclicalkyl and tri Including cycloalkyl), perhaloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, azide, amine, ketone, ether, amide, ester, triazole, isocyanate, arylalkyloxy, aryloxy, Mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N- Amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, cyryl, trihalomethanesulfonyl, Pyrrolidinone, pyrrolidine, piperidine, piperazine, morpholine, amine, amino, amido, nitro, ether, ester, halogen, thiol, aldehyde, carbonyl, phosphorus, sulfur, phosphate, phosphat, phosphine When substituted with one or more groups individually and independently selected from amino, including pit, sulfate, disulfide, oxy, mercapto and hydrocarbyl mono- and di-substituted amino groups, and protective derivatives thereof Including, without being limited thereto, it is meant to comprehensively include a case substituted by various substituents commonly used in the art. In some cases, these may also be substituted or unsubstituted.

The term "heteroatom" means an atom other than carbon and hydrogen.

The term “heteroalkyl” refers to a form in which at least one of the carbon atoms of an alkyl group is substituted with another hetero atom.

The organometallic precursor compound of the present invention and the organometallic thin film prepared using the same satisfy high volatility, excellent chemical and thermal stability, and have a remarkably improved thin film deposition rate even at low temperatures.

In addition, by providing an organometallic precursor compound that can be used to form a dielectric thin film in a semiconductor device, an organometallic deposition layer or a thin film including a metal deposition layer having improved characteristics deterioration due to by-products may be manufactured.

^{1 and 2 are respectively 1} H NMR and ¹³ C NMR measurement results of the tungsten precursor compound synthesized in Example 1.
3 is a TGA analysis result of a tungsten precursor compound synthesized in Example 1-1.
4 is a graph showing resistivity and deposition rate measurements according to RF voltage intensity of the ALD-deposited tungsten thin film of Preparation Example 1-1.
5 is a graph showing resistivity and deposition rate measurement according to purge time of the ALD-deposited tungsten thin film of Preparation Example 1-1.
6 is an EDS measurement graph according to the RF voltage intensity of the ALD-deposited tungsten thin film of Preparation Example 1-1.
^{7 is a 1} H NMR and ¹³ C NMR measurement results of the molybdenum precursor compound synthesized in Example 2-1.
8 is a TGA analysis result of the molybdenum precursor compound synthesized in Example 2-1.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present invention. However, the examples do not limit the scope of the present invention, which should be construed to aid understanding of the present invention.

As described above, the conventional organometallic precursor compound has a limitation in the semiconductor mass production process due to a low thin film deposition rate, and due to low chemical and thermal stability, step coverage due to decomposition of the precursor at a high substrate temperature during deposition due to low chemical and thermal stability. It is degraded, and there is a problem in that the properties are deteriorated by the process and by-products of the deposited thin film, and the reliability and efficiency of the process are low.

Accordingly, the present invention seeks to solve the above-described problems by providing an organometallic precursor compound represented by Formula 1 below. Through this, there is an effect of providing an organometallic precursor compound that satisfies high volatility, excellent chemical and thermal stability, and has an effect of having a remarkably improved thin film deposition rate even at a low temperature. In addition, there is an advantage in that it is possible to provide a thin film including an organometallic deposition layer or a metal deposition layer with improved characteristics deterioration due to by-products.

[Formula 1]

이다. In Formula 1, M is a tungsten atom (W), a chromium atom (Cr) or a molybdenum atom (Mo), R ₁ is a C _{2 to 10} alkylene group or a heteroalkylene group, and R ₂ is C _{1 to 5} An alkylene group or a heteroalkylene group, R ₃ and R ₄ are each independently a C _1-10 alkyl group, X is a nitrogen atom (N), a phosphorus atom (P), an arsenic atom (As) or

to be.

As described above, the organometallic precursor compound according to the present invention has _{a structure that forms a ring with cyclopentadiene (Cp, cyclopentadiene), M, R 1} and X, and through the formation of such a ring structure, the thin film deposition is significantly improved even at low temperatures. It is possible to provide a tungsten precursor having a velocity. In addition, the organometallic precursor compound may be used to prepare an organometallic thin film having improved properties due to by-products.

이며, 바람직하게는 N, P 또는

일 수 있고, 보다 바람직하게는 N일 수 있다. Meanwhile, M in Formula 1 may be a tungsten atom (W), a chromium atom (Cr), or a molybdenum atom (Mo), and preferably a tungsten atom or a molybdenum atom. In addition, X in Formula 1 is a nitrogen atom (N), a number of atoms (P), an arsenic atom (As), or

And, preferably N, P or

May be, more preferably N.

In addition, R ₁ in Formula 1 is a C _{2 to 10} alkylene group or a heteroalkylene group, preferably a C _{2 to 5} alkylene group, more preferably a C _{2 to 3} alkylene group, and , Most preferably may be -(CH ₂ )-. Through this, it is possible to provide a high-purity organic metal-containing thin film with improved characteristics deterioration due to by-products. If R ₁ is a C ₁ alkylene group or a heteroalkylene group, it is difficult to deposit a high-purity tungsten-containing thin film, and accordingly, characteristics of the thin film may be deteriorated due to by-products.

_{The meaning of R 1 in} Formula 1 is a C _{2 to 10} alkylene group or a heteroalkylene group, wherein R ₁ is a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted heterogeneous group having 2 to 10 carbon atoms. It means that it is an alkylene group. More specifically, the _{meaning of a C 2-10} heteroalkylene group does not mean that the total number of carbons and heteroatoms is 2-10, but means that the number of carbons excluding heteroatoms is 2-10.

In the heteroalkylene group, the hetero atom may be widely selected as long as it is an atom capable of forming a stable substituent by bonding with a carbon atom in an alkyl group, but preferably a nitrogen atom (N), an oxygen atom (O), or a sulfur atom ( It can be S).

In addition, the number of heteroatoms in the heteroalkylene group is not limited as long as it contains 2 to 10 carbons and can form a stable organometallic compound, but it may be preferably 1 to 8, and more preferably It may be 1 to 4, more preferably 1 to 2 may be.

In addition, the R ₂ of Formula 1 is a C _1-5 alkyl group or a heteroalkyl group, preferably a C _{1 to 3} alkyl group, more preferably a C _{1 to 2} alkyl group, more preferably May be -CH _3.

The _{meaning that R 2} is a C _1-5 alkyl group or a heteroalkyl group means that R ₂ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms or a substituted or unsubstituted heteroalkyl group having 1 to 5 carbon atoms. More specifically, _{the meaning of a C 1-5} heteroalkyl group does not mean that the total number of carbons and heteroatoms is 1-5, but means that the number of carbons excluding heteroatoms is 1-5.

In the _{heteroalkyl group of R 2,} the hetero atom may be widely selected as long as it is an atom capable of forming a stable substituent by bonding with a carbon atom in the alkyl group, but preferably a nitrogen atom (N), an oxygen atom (O), or sulfur It may be an atom (S).

In addition, the _{number of heteroatoms in the heteroalkyl group of R 2} is not limited as long as it contains 1 to 5 carbons and can form a stable organometallic compound, but it may be preferably 1 to 3, More preferably, it may be 1 to 2, and more preferably, it may be 1.

Meanwhile, R ₃ and R ₄ in Formula 1 may each independently be a C _{1 to 10} alkyl group, and preferably each independently may be a _{C 1 to 5 alkyl group.} More preferably, each independently may be a C1-4 alkyl group, and may be selected from CH ₃ , C ₂ H ₅ , C ₃ H ₇ , iC ₃ H ₇ , nC ₄ H ₉ , tC ₄ H ₉ , and most Preferably it may be tC ₄ H ₉ .

The meaning that each of the above may exist independently means that different substitution units, R ₃ and R ₄ , may be selected from the same or different substituents.

Hereinafter, it will be described in detail excluding the overlapping content.

In addition, the present invention provides an organometallic precursor compound represented by the following formula (2). Through this, it is possible to deposit a high-purity thin film, thereby obtaining a thin film with improved characteristics deterioration due to by-products.

[Formula 2]

In Formula 2, M is a tungsten atom (W), a chromium atom (Cr), or a molybdenum atom (Mo), preferably a tungsten atom or a molybdenum atom. In Formula 2, R ₁ ′ is a C _{1 to 4} alkylene group or a heteroalkylene group, R ₂ is a C _{1 to 5} alkyl group or heteroalkyl group, and R ₃ and R ₄ are each independently a C _{1 to 10} alkyl group to be.

The R ₁ ′ in Formula 2 is a C _{1 to 4} alkylene group or a heteroalkylene group, preferably a C _{1 to 3} alkylene group, more preferably a C _{1 to 2} alkylene group or a heteroalkylene group. It may be a group, and most preferably may be -(CH ₂ )-.

The _{meaning of R 1} ′ is a C _{1 to 4} alkylene group or a heteroalkylene group, R ₁ ′ is a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, or a substituted or unsubstituted heteroalkyl having 1 to 4 carbon atoms It means that it is Rengi. More specifically, _{the meaning of a C 1-4} heteroalkylene group does not mean that the total number of carbons and heteroatoms is 1-4, but means that the number of carbons excluding heteroatoms is 1-4.

Likewise, the _{meaning of R 1} ′ is a C _{1 to 2} alkylene group or a heteroalkylene group means that R ₁ ′ is a substituted or unsubstituted alkylene group having 1 to 2 carbon atoms, or a substituted or unsubstituted hetero group having 1 to 2 carbon atoms. It means that it is an alkylene group. In addition, the _{meaning of the C 1 to 2} heteroalkylene group does not mean that the total number of carbons and heteroatoms is 1 to 2, but means that the number of carbons excluding hetero atoms is 1 to 2.

In the heteroalkylene group, the hetero atom may be widely selected as long as it is an atom capable of forming a stable substituent by bonding with a carbon atom in the alkyl group, but it may be preferably N, O or S.

In addition, the number of heteroatoms in the heteroalkylene group is not limited as long as it contains 1 to 4 carbons and can form a stable organometallic compound, but it may be preferably 1 to 6, and more preferably It may be 1 to 3, more preferably 1 to 2.

In addition, the R ₂ in Formula 2 is a C _1-5 alkyl group or a heteroalkyl group, preferably a C _1-3 alkyl group, more preferably a C _1-2 alkyl group, and most preferably May be CH _3.

_{The meaning of R 2} in Formula 2 as a _{C 1-5} alkyl group or heteroalkyl group means that R ₂ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms or a substituted or unsubstituted heteroalkyl group having 1 to 5 carbon atoms. . More specifically, _{the meaning of a C 1-5} heteroalkyl group does not mean that the total number of carbons and heteroatoms is 1-5, but means that the number of carbons excluding heteroatoms is 1-5.

In the heteroalkyl group of Formula 2, the hetero atom may be widely selected as long as it is an atom capable of forming a stable substituent by bonding with a carbon atom in the alkyl group, but it may be preferably N, O or S.

In addition, the number of heteroatoms in the heteroalkyl group of Formula 2 is not limited as long as it contains 1 to 5 carbons and can form a stable organometallic compound, but it may be preferably 1 to 6, More preferably, it may be 1 to 3, and more preferably, it may be 1 to 2.

Meanwhile, R ₃ and R ₄ in Formula 2 may each independently be a C _1-10 alkyl group, and preferably each independently a C _1-5 alkyl group. More preferably, each independently may be a C _1-4 alkyl group, and may be selected from CH ₃ , C ₂ H ₅ , C ₃ H ₇ , iC ₃ H ₇ , nC ₄ H ₉ , tC ₄ H ₉ , Most preferably, it may be tC ₄ H ₉ .

The meaning that each of the above may exist independently means that different substituent units R ₃ and R ₄ may be selected from the same or different substituents.

In addition, the present invention provides an organometallic precursor compound represented by the following formula (3). Through this, there is an effect of providing an organometallic precursor compound that satisfies high volatility, excellent chemical and thermal stability, and has an effect of having a remarkably improved thin film deposition rate even at a low temperature. In addition, there is an advantage of providing a tungsten-containing thin film with improved characteristics deterioration due to by-products.

[Formula 3]

In Formula 3, M is a tungsten atom (W), a chromium atom (Cr), or a molybdenum atom (Mo), preferably a tungsten atom or a molybdenum atom. In addition, R ₂ is a C _{1 to 3} alkyl group, and R ₃ and R ₄ are each independently a C _{1 to 5} alkyl group.

In Formula 3, R ₂ may be a C _{1 to 3} alkyl group, preferably a C _{1 to 2} alkyl group, and more preferably CH ₃ .

In addition, the R ₃ and R ₄ of Formula 3 are each independently _{an alkyl group of C 1 to 5} , preferably each independently may be an alkyl group of C _{1 to 4} , -CH ₃ , -C ₂ H ₅ ,- It may be selected from C ₃ H ₇ , iC ₃ H ₇ , nC ₄ H ₉ , tC ₄ H _{9 , and most preferably tC 4} H ₉ .

The organometallic precursor compound represented by Formula 3 may be preferably represented by an organometallic precursor compound represented by Formula 4 below.

[Formula 4]

In Formula 4, M is a tungsten atom (W), a chromium atom (Cr), or a molybdenum atom (Mo), preferably a tungsten atom or a molybdenum atom, and R ₃ and R ₄ are each independently C _{3 to 5} It is an alkyl group of.

In addition, the present invention provides an organometallic precursor compound, characterized in that represented by the following formula (5). Through this, there is an effect of providing an organometallic precursor compound that satisfies high volatility, excellent chemical and thermal stability, and has an effect of having a remarkably improved thin film deposition rate even at a low temperature. In addition, there is an advantage in that it is possible to provide an organometallic-containing thin film with improved characteristics deterioration due to by-products.

[Formula 5]

In Formula 5, M is a tungsten atom (W), a chromium atom (Cr), or a molybdenum atom (Mo), preferably a tungsten atom or a molybdenum atom.

In addition, the organometallic precursor compound may be widely used as long as it is generally used, but preferably may be included or used in the process of manufacturing a semiconductor material in the semiconductor field. In addition, more preferably, it may be used for manufacturing an organic metal-containing thin film for semiconductors.

Specifically, the organometallic precursor compounds may be used as precursors for forming a thin film included in a semiconductor. A precursor refers to a material in a step before becoming a specific material in metabolism or reaction, and a thin film used for a semiconductor may be formed by physical/chemical adsorption of the organometallic precursor compound on a substrate.

In addition, the present invention provides an organic metal-containing thin film or a metal-containing thin film prepared by including any one of the organometallic precursor compounds as a precursor. Through this, it is possible to provide a thin film containing high-purity tungsten, chromium, or molybdenum containing little or no by-products, thereby improving characteristics degradation due to by-products.

Specifically, in the case of manufacturing an organometallic-containing thin film by including the organometallic precursor compound of the present invention as a precursor, the organometallic precursor compound of the present invention may be included in the organometallic thin film as it is, or the final form may be modified during the process. have. That is, when the organometallic precursor compound of the present invention is used as a precursor to prepare a thin film included in a semiconductor, the final form may exist in various ways.

Further, the present invention provides a step of a) providing a vapor including any one of the organometallic precursor compounds, and b) reacting the vapor with a substrate according to a deposition method, thereby comprising organometallic on at least one surface of the substrate. It provides a method for producing an organometallic thin film comprising the step of forming a complex layer (deposition layer) or a metal-containing complex layer (deposition layer).

When the above manufacturing method is used, the substrate adsorption efficiency can be improved and the safety can be increased at the same time when the substrate is formed, and the process speed can be shortened by increasing the thin film deposition rate. In addition, it can be used in a wide temperature range while reducing the contamination in the process, and can significantly improve the reliability and efficiency of the manufacturing process. Furthermore, through the above manufacturing method, it is possible to obtain a thin film with improved characteristics deterioration due to by-products, excellent uniformity, and improved stepped film characteristics.

Hereinafter, description will be made in detail except for the content overlapping with the above-described content.

First, a) a step of providing a vapor including any one of the organometallic precursor compounds will be described.

Evaporation of the metal source is realized by introducing a carrier gas into a heated vessel containing the organometallic precursor compound of the present invention as a metal source. The vessel is preferably heated to a temperature such that the metal source can be obtained with sufficient vapor pressure. The carrier gas may be selected from Ar, He, H ₂ , N _{2 or mixtures thereof.} In a vessel the metal source may be mixed with a solvent or another metal source or mixtures thereof. The container may preferably be heated at a temperature in the range of 25° C. to 200° C., and the amount of evaporated precursor may be controlled by adjusting the temperature of the container. The pressure in the vessel can be changed to control the level of evaporation in the vessel. By reducing the pressure in the vessel, the level of evaporation of the metal source can be increased. Preferably, the pressure in the vessel may vary in the range of 1 Torr to 800 Torr.

In addition, the metal source may be supplied to an evaporator in which evaporation occurs in a liquid state. The metal source may not be mixed with a solvent or may be mixed. It is also possible to mix the metal source with another metal source. The mixture of the metal source may be mixed with a solvent or a solvent mixture. The metal source can be mixed with a stabilizer. The solvents are alkanes such as hexane, heptane, octane, aromatic solvents such as benzene, toluene, mesitylene, xylene, silicon containing solvents such as hexamethyldisiloxane, hexamethyldisilazane, tetramethylsilane, sulfur containing solvents such as It may be selected from the group consisting of dimethyl sulfoxide, an oxygen-containing solvent such as tetrahydrofuran and dioxane. Meanwhile, the concentration of the mixed solution including the solvent may preferably include 50 to 99.9% by weight of the metal source.

Next, a step of b) reacting the vapor with a substrate according to a deposition method to form a layer of a tungsten-containing complex on at least one side of the substrate will be described.

The vaporized metal source is introduced into a reaction chamber, where it is brought into contact with the surface of the substrate. The substrate can be heated to a temperature sufficient to obtain a desired thin film having the desired physical state and composition at a sufficient growth rate. The heating temperature may be generally heated to a temperature for obtaining a desired thin film, but may preferably be in the range of 100°C to 700°C, and more preferably 450°C or less. On the other hand, the process may be assisted by a plasma technique selected without limitation in order to improve the reactivity of the vaporized metal source and/or other gas species used in the process.

Meanwhile, the deposition method in step b) is not limited as long as it is a method capable of forming an organometallic-containing complex layer (deposition layer) or a metal-containing complex layer (deposition layer) on the surface of the substrate, but is preferably a chemical vapor phase. A chemical vapor deposition (CVD) or atomic layer deposition (ALD) method may be used.

First, the atomic layer deposition method (ALD) is a method of growing a thin film by cross-injecting a raw material containing a metal and a reaction gas (for example, NH _3, etc.), and growing an atomic unit thin film by reacting the raw material and the gas. This is a method of repeatedly adjusting the thickness of the thin film. Specifically, the organometallic precursor compound according to the present invention may be injected into the vaporizer and then transferred to the chamber in a vapor phase. The vaporized film-forming composition can be transferred to the chamber. In this case, the delivery method of the precursor material is a method of transferring the vaporized gas using vapor pressure, a direct liquid injection method, or a liquid delivery system (LDS) in which the precursor material is dissolved in an organic solvent and transferred. Can be used. In this case, the transport gas or the dilution gas for moving the precursor material onto the substrate may preferably _{use at least one inert gas selected from Ar, N 2} , He or H ₂ , and more preferably from Ar or N ₂ Can be chosen. Meanwhile, the _{flow rate of the N 2} canister may be preferably in the range of 30 to 200 sccm, and more preferably in the range of 50 sccm to 100 sccm.

Next, the transferred precursor material may be supplied and adsorbed onto the substrate, and the unadsorbed precursor material may be purged. An inert gas may be used as the purge gas. Next, a reactant can be supplied. The reactant may include an oxidizing agent such as _{H 2} O, H ₂ O ₂ , O ₂ , O ₃ , and N _{2 O.} The reactant and the precursor material may react to form an organometallic and/or metal-containing thin film, and the thin film may include tungsten, chromium, or molybdenum. Next, the unreacted material is purged. Accordingly, an excessive amount of reactants and generated by-products can be removed.

Meanwhile, the precursor material supply step, purge, reactant supply step, and purge are used as unit cycles. In order to form a thin film of the desired thickness, the unit cycle can be repeated. Preferably, it can be carried out by repeating 10 to 10,000 cycles.

Further, in the case of using the atomic layer deposition method, the temperature may preferably be in the range of 100°C to 450°C, more preferably in the range of 150°C to 350°C. In ALD, the purge time is preferably 1 to 10 seconds, and the pressure may be preferably 0.01 Torr to 800 Torr.

For a specific example, the ALD-deposited thin film using the organometallic precursor compound of the present invention has a thin film deposition rate of more than 0.7 Å/cycle, preferably 0.95 to 1.5 Å/cycle, preferably 1.05 to 1.55 Å/cycle. Can be satisfied. The specific resistance value (resistivity) is 3.0ⅹ10 ^-3 Ω · ㎝, preferably less than ^{1.9 × 10 -3 ~ 2.9 × 10} -3 Ω · ㎝, more preferably from ^{2.0 × 10 -3 ~ 2.4 × 10} -3 Ω·cm can be satisfied. In addition, it is possible to provide a high purity ALD deposited thin film by including 12.5 at% or less, preferably 11.0 at% or less, and more preferably 7.0 at%, of carbon (C), which is an impurity.

Next, in the chemical vapor deposition method (CVD), a gas containing an element constituting the thin film material to be formed is supplied onto a substrate, and the substrate is subjected to chemical reactions such as thermal decomposition, photolysis, redox reaction, and substitution in the gas phase or the substrate surface. It is a method of forming a thin film on the surface. In the case of using the chemical vapor deposition method, the temperature may preferably be in the range of 100°C to 700°C, and more preferably in the range of 200°C to 500°C. In addition, the pressure may be preferably 0.01 Torr ~ 800 Torr, more preferably 1 Torr ~ 200 Torr range. In addition, the carrier gas may be preferably N ₂ , He, Ar, H ₂ , and more preferably may be selected from _{Ar or N 2.} A preferred N ₂ canister flow rate may range from 30 to 200 sccm, more preferably from 50 sccm to 100 sccm.

Furthermore, the present invention contains 0.1% to 99.9% of any one or more of the organometallic precursor compounds, and contains saturated or unsaturated hydrocarbons, cyclic ethers, acyclic ethers, esters, alcohols, cyclic amines, and non-cyclic A composition containing the residual amount of one or more organic compounds selected from amines, cyclic sulfides, acyclic sulfides, phosphines, beta-dikitones, and beta-chitoesters, and a metal-containing thin film using the composition Provides a way to do it.

In the case of manufacturing a thin film using a composition containing the organometallic precursor compound, there is an effect of increasing the efficiency and safety of adsorption of the compound to the substrate and shortening the process time. In addition, since the physical properties and composition of the thin film prepared by adjusting the content of the composition can be adjusted, a thin film suitable for the purpose and means can be easily prepared.

As a result, the present invention provides an organometallic precursor compound and a thin film manufactured using the same, so that 1) reliability and efficiency of the manufacturing process can be increased, as well as 2) improved chemical and thermal stability, and 3) this At the same time, a significantly improved thin film deposition rate can be achieved even at low temperatures. In addition, the excellent organometallic precursor compound as described above can be used to manufacture a thin film for a semiconductor, through which the present invention has improved properties due to by-products, has excellent step coverage, and has a high dielectric constant, so that it is electrically equivalent oxide film. It is possible to provide an organic metal-containing and/or metal-containing thin film for semiconductors having a thickness that does not physically cause tunneling while having a thickness (EOT), and a semiconductor structure including the same.

Hereinafter, examples for synthesizing the compound represented by Chemical Formula 1 included in the precursor of the present invention and an example for forming a film using the same will be described in detail with examples, but are not limited to the following examples of the present invention.

[Example]

Example 1-1: Synthesis of tungsten (W) precursor compound

The reaction of the following steps (1), (2) and (3) was sequentially performed to prepare a compound represented by the following formula 1-1.

(1) (1) step ((t-bytyl-N=) _{2 of} WCl ₂ synthesis)

_{Add 100g (0.252mol, 1.00 equiv) of WCl 6} to a 2L Schlenk flask containing 500ml of toluene, cool it to -50℃ or less with stirring, and then n-tert-butyl trimethylsilyl amine (n-tert-butyl trimethylsilyl amine) 146.5 g (1.008 mol, 4.00 equivalent) was added for 5 hours. The mixed reaction solution was slowly heated to room temperature, stirred at room temperature for 12 hours, and the reaction was terminated. The resulting solid was filtered, and then the solvent was completely removed under reduced pressure. 100g (yield: 84%) of the first step product was obtained.

(2) Step 2 (Synthesis of (t-bytyl-N=) ₂ W(NMe ₂ ) ₂ ): In a 2L Schlenk flask containing 500 ml of hexane (t-bytyl-N=) ₂ WCl ₂ 100 g (0.213) mol, 1.00 equiv) was added and cooled to -50°C or less while stirring, and then 27.1 g (0.531 mol, 2.50 equiv) of Li (AMD) was added for 1 hour. The reaction mixture was stirred at room temperature for 3 hours to terminate the reaction. The resulting solid (LiCl) was filtered, and then the solvent was completely removed under reduced pressure. The resulting liquid was distilled under reduced pressure (70° C./0.2 torr) to give 36 g (yield: 38%) of a red liquid compound.

(3) Step 3 (Synthesis of (CpCH ₂ CH ₂ NCH ₃ )W(=Nt-bytyl) ₂ ): (+N=)2W(NMe) synthesized in step 2 in a 2L Schlenk flask containing 500ml of hexane. ₂ ) ₂ 36g (0.087 mol, 1.00 equiv) was added, cooled to -50°C with stirring, and then cyclopentadienylethylmethylamine (CpCH ₂ CH ₂ NCH ₃ ) was added for 1 hour. The mixed reaction solution was stirred at room temperature for 5 hours to terminate the reaction. Subsequently, after completely removing the solvent under reduced pressure, the resulting liquid was distilled under reduced pressure (boiling point: 100°C, 0.2torr) to 25 g of a tungsten precursor compound (CEMAW), a compound represented by the following Formula 1-1, which is the title compound of a yellow liquid. (Yield 64%) was obtained.

In addition, ¹ H NMR and ¹³ C NMR analysis results for the ^{prepared CEMAW are shown in FIGS. 1 (1} H NMR) and 2 ( ¹³ C NMR), respectively.

In addition, the result of TGA analysis for the prepared compound is shown in FIG. 3.

[Formula 1-1]

In Formula 1-1, M is a tungsten atom (W), X is a nitrogen atom, R ₁ is -(CH ₂ CH ₂ )-, R ₁ is a methyl group, and R ₃ and R ₄ are t-butyl groups. .

Examples 1-2 to 1-16

A tungsten precursor compound having the structure of the following Formula 1, wherein X, R ₁ , R ₂ , R ₃ and R _{4 are determined according to Tables 1 to 3 was synthesized.}

division Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Example 1-6 M W W W W W W X N P

As N N R ₁ -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ CH ₂ )- -(CH ₂ CH ₂ OCH ₂ )- R ₂ -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₃ R ₃

R ₄

division Example 1-7 Example 1-8 Example 1-9 Example 1-10 Example 1-11 Example 1-12 M W W W W W W X N N N N N N R ₁ -(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ )- -(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- R ₂ -CH ₃ -CH ₃

R ₃

R ₄

division Example 1-13 Example 1-14 Example 1-15 Example 1-16 M W W W W X N N N N R ₁ -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- R ₂ -CH ₃ -CH ₃ -CH ₃ -CH ₃ R ₃ -CH ₃

R ₄ -CH ₃

Comparative Example 1-1

A compound represented by the following formula (6) was synthesized.

[Formula 6]

Comparative Example 1-2

A compound represented by the following formula (7) was synthesized.

[Formula 7]

Preparation Example 1-1: Formation of tungsten thin film using atomic layer deposition (ALD)

Using the organometallic precursor compound (CEMAW) prepared in Example 1-1, an atomic layer deposition method was performed to form a tungsten thin film. The ALD deposition conditions in which CEMAW is used as a first cycle in which the precursor supply step-first purge-reactant supply step-second purge is performed on the substrate are shown in Table 4 below.

division Condition ALD evaporation equipment PEALD (Isac Research, model name: IOV-D300) Precursor delivery method LDS type Cycle time *Tungsten precursor supply time: 3 seconds
*1st purge time: 3 seconds to 10 seconds
*Reactive substance (NH ₃ ) supply time: 3 seconds
*2nd purge time: 3 seconds to 10 seconds Number of cycles 500 cycles RF voltage (power) strength 300 to 700 W (PEALD) Flow rate LFM (0.05 g/min), NH ₃ (200 sccm) Working pressure 1.0 ~ 1.5 Torr Board 12”Si wafer Temperature *Substrate = 400℃
*Canister: room temperature (LDS)
* Vaporizer: 140℃
*Transfer line: 140℃

Experimental Example 1: Resistivity, deposition rate, and EDS analysis of ALD-deposited tungsten thin film

The resistivity, deposition rate, and EDS of the thin film were analyzed, and the results are shown in Table 5 below. In addition, measurement values of the specific resistance and deposition rate according to the RF voltage are shown in FIG. 4. In this case, the measured values in FIG. 4 are measured when the cycle time is 3 seconds/5 seconds/3 seconds/5 seconds of the tungsten precursor supply/first purge/reactant supply/second purge time. And, when the RF voltage intensity is 700W, the specific resistance and deposition rate measured values according to the change of the purge time are shown in FIG. 5. In addition, when the tungsten precursor supply/first purge/reactant supply/second purge time is 3 seconds/5 seconds/3 seconds/5 seconds, the EDS measurement results according to the RF voltage intensity are shown in FIG. 6.

4, as the RF voltage intensity increases, the thin film deposition rate tends to decrease, and when the specific resistance value is 300W, it is the highest, the lowest at 500W, and it is confirmed that the specific resistance value increases again after 500W. I can. That is, a specific resistance value of ^{less than 3.0×10 -3} Ω·cm, preferably 2.0×10 ^-3 to 2.9×10 ^-3 Ω·cm, satisfies an RF voltage intensity of 400W to 750W, preferably 450W to 600W. I can confirm.

And, looking at Figure 5, when the RF voltage intensity is 700W, as the purge time increases, the resistivity and the thin film deposition rate decrease and then increase again, and the appropriate purge time is preferably 3 to 6 seconds, or 8 seconds. It is preferable that it is from seconds to 10 seconds, and it will be more preferable that it is from 3 to 6 seconds in consideration of economical efficiency.

In addition, referring to FIG. 6, it can be seen that the content of carbon (C) and nitrogen (N) tends to decrease as the RF voltage intensity increases, and the carbon concentration, which is an impurity in the thin film, is 5.0 to 12.5 at%. I could confirm that. And, through the low nitrogen content, it was confirmed that the W=N double bond in the thin film was firmly bonded without being broken.

Considering the low resistivity value, high thin film deposition rate, and low impurity content, when comprehensively judged, the ALD deposition process conditions using CEMAW are RF voltage strength of 400 to 750W, preferably 450W to 600W, and purge ) It can be seen that the time of about 3 to 6 seconds is advantageous for the thin film formation conditions.

Preparation Examples 1-2 to 1-16 and Comparative Examples 1-1 to 1-2

A tungsten thin film was formed through the ALD deposition process in the same manner as in Preparation Example 1-1, but RF voltage was applied using the tungsten compounds of Examples 1-2 to 1-16 and Comparative Examples 1-1 to 1-2, respectively. A tungsten thin film was formed by performing 500 cycles of 500 W of intensity and CEMAW on the substrate with a precursor supply step-first purge-reactant supply step-second purge as one cycle of 3 seconds/5 seconds/3 seconds/5 seconds. .

Experimental Example 2: Resistivity, deposition rate, and EDS analysis of ALD-deposited tungsten thin film

Resistivity, thin film deposition rate, and EDS analysis (carbon content, at%) of the tungsten thin films of Preparation Examples 1-1 to 1-16 and Comparative Examples 1-1 to 1-2 were performed in the same manner as in Experimental Example 1, The results are shown in Table 5 below.

division Resistivity value (Ω·cm) Thin film deposition rate (Å/cycle) Impurity concentration Carbon (at%) Manufacturing Example 1-1 (2.2 ~ 2.3)×10 ^-3 1.05 ~ 1.10 10.5 ~ 11.0 Preparation Example 1-2 (2.4 ~ 2.5)×10 ^-3 1.03 ~ 1.08 9.8 ~ 10.3 Manufacturing Example 1-3 (2.3 ~ 2.4)×10 ^-3 1.05 ~ 1.10 11.5 ~ 12.0 Manufacturing Example 1-4 (2.7 ~ 2.8)×10 ^-3 0.95 ~ 1.00 8.8 ~ 9.3 Manufacturing Example 1-5 (2.4 ~ 2.5)×10 ^-3 1.00 to 1.05 9.0 ~ 9.5 Preparation Example 1-6 (2.5 ~ 2.6)×10 ^-3 1.05 ~ 1.10 10.8 ~ 11.3 Manufacturing Example 1-7 (2.5 ~ 2.6)×10 ^-3 0.90 ~ 0.95 10.5 ~ 11.0 Manufacturing Example 1-8 (2.6 ~ 2.7)×10 ^-3 0.85 ~ 0.90 10.9 ~ 11.4 Manufacturing Example 1-9 (2.4 ~ 2.5)×10 ^-3 1.20 ~ 1.25 8.8 ~ 9.3 Preparation Example 1-10 (2.5 ~ 2.6)×10 ^-3 1.25 ~ 1.30 9.0 ~ 9.5 Manufacturing Example 1-11 (2.5 ~ 2.6)×10 ^-3 1.17 ~ 1.22 10.0 ~ 10.5 Preparation Example 1-12 (2.4 ~ 2.5)×10 ^-3 1.00 to 1.05 11.0 ~ 11.5 Manufacturing Example 1-13 (1.9 ~ 2.0)×10 ^-3 1.30 ~ 1.35 5.5 to 6.0 Preparation Example 1-14 (2.1 ~ 2.2)×10 ^-3 1.25 ~ 1.30 5.5 to 6.0 Manufacturing Example 1-15 (2.2 ~ 2.3)×10 ^-3 1.10 ~ 1.15 8.5 to 9.0 Manufacturing Example 1-16 (2.6 ~ 2.7)×10 ^-3 0.95 ~ 1.00 7.5 ~ 8.0 Comparative Production Example 1-1 (2.4 ~ 2.5)×10 ^-3 1.00 to 1.05 14.5 ~ 15.0 Comparative Production Example 1-2 (3.2 ~ 3.3)×10 ^-3 0.70 ~ 0.75 16.7 ~ 17.2

According to Table 5, the thin film deposition rates of thin films prepared by using the tungsten compound as a precursor among the organometallic compounds of the present invention all exceed 0.7 Å/cycle, preferably 0.95 to 1.5 Å/cycle, preferably 1.05 to It can be confirmed that it satisfies 1.55Å/cycle and has an excellent thin film deposition rate, and the specific resistance value is ^{less than 3.0x10 -3} Ω·cm, preferably 1.9×10 ^-3 to 2.9×10 ^-3 Ω·cm, more preferably It can be seen that it satisfies 2.0×10 ^-3 ~ 2.4×10 ^{-3 Ω·cm.}

Furthermore, even in the case of thin film purity, all carbons as pollutants are 12.5 at% or less, preferably 11.0 at% or less, and through this, the present invention can provide a thin film with improved purity due to a significantly lower amount of residual impurities Able to know.

On the other hand, Comparative Example 1-1 had a problem with a high carbon impurity content, and Comparative Example 1-2 not only had a clogging phenomenon during ALD deposition, but also showed a higher resistivity value and a lower thin film deposition rate than that of Preparation Example.

Example 2-1: Synthesis of molybdenum (Mo) precursor compound

The reaction of steps (1), (2) and (3) was sequentially performed to prepare a compound represented by the following formula 2-1.

(1) (t-bytyl-N=) ₂ MoCl ₂ of synthesis

_{MoO 2} Cl ₂ (25g) was subdivided into a 2L Schlenk flask, and acetonitrile was added thereto. After stirring, tert -Butyl Isocyanate was added dropwise. Next, after stirring at room temperature, reflux was performed for 12 hours. Next, after stripping the solvent t, it was turned on by recrystallization. (+N=) ₂ 37g of MoCl ₂ was synthesized (yield: 93%).

(2) (t-bytyl-N=) ₂ Mo(NMe ₂ ) ₂ of synthesis

_{Add (+N=) 2} MoCl ₂ (1.00 eq) to a 2L Schlenk flask containing 500ml of hexane, cool it to -50℃ or less while stirring, and slowly add Li(AMD) (2.50 eq) for 1 hour. I did. Next, it was stirred at room temperature for 3 hours to terminate the reaction. The resulting solid (LiCl) was filtered, and then the solvent was completely removed under reduced pressure. The resulting liquid was distilled under reduced pressure (70° C./0.2 torr) _{to synthesize (+N=) 2} Mo(NMe ₂ ) ₂ 33 g (yield 80%).

(3) CpCH ₂ CH ₂ NCH ₃ )Mo(=N-t-bytyl) ₂ of synthesis

In a 2L Schlenk flask containing 500ml of hexane, add (+N=) ₂ Mo(NMe ₂ ) ₂ (1.00 equivalent) synthesized in step 2, cool to -50°C with stirring, and then cyclopentadienylethylmethylamine (CpCH ₂ CH ₂ NCH ₃ ) was slowly added for 1 hour. Next, it was stirred at room temperature for 5 hours to terminate the reaction. Subsequently, after completely removing the solvent under reduced pressure, the resulting liquid was distilled under reduced pressure (boiling point: 100°C, 0.1 torr), and 20 g of a molybdenum precursor compound, a compound represented by the following formula 1-2, which is a dark yellow liquid (yield 60%).

In addition, ¹ H NMR and ¹³ C NMR analysis results for the ^{prepared CEMAW are shown in Fig. 7 (1} H NMR)), and the TGA analysis results are shown in Fig. 8.

[Formula 1-2]

In Formula 1-2, M is a molybdenum atom (Mo), X is a nitrogen atom, R ₁ is -(CH ₂ CH ₂ )-, R ₁ is a methyl group, and R ₃ and R ₄ are t-butyl groups. .

Examples 2-2 to 2-12

A molybdenum precursor compound having the structure of Formula 2-1 and in which X, R ₁ , R ₂ , R ₃ and R _{4 are determined according to Tables 6 to 7 was synthesized.}

division Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Example 2-6 M Mo Mo Mo Mo Mo Mo X N P

As N N R ₁ -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ CH ₂ )- -(CH ₂ CH ₂ OCH ₂ )- R ₂ -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₃ R ₃

R ₄

division Example 2-7 Example 2-8 Example 2-9 Example 2-10 Example 2-11 Example 2-12 M Mo Mo Mo Mo Mo Mo X N N N N N N R ₁ -(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ )- -(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- -(CH ₂ CH ₂ )- R ₂ -CH ₃ -CH ₃

R ₃

R ₄

Comparative Example 2-1

A compound represented by the following formula (8) was synthesized.

[Formula 8]

Preparation Examples 2-1 to 2-12 and Comparative Preparation Example 2-1

Each of the molybdenum (Mo) precursor compounds of Examples 2-1 to 2-12 and Comparative Example 2-1 under the same conditions and methods as in Preparation Example 1-1, by forming a molybdenum thin film using an atomic layer deposition method (ALD), Preparation Examples 2-1 to 2-12 and Comparative Preparation Example 2-1 were carried out, respectively. At this time, at the time of deposition, the ALD deposition conditions of one cycle are shown in Table 4 above.

Experimental Example 3: Specific resistance, deposition rate, EDS analysis of ALD-deposited molybdenum thin film

Resistivity, thin film deposition rate, and EDS analysis (carbon content, at%) of the molybdenum thin films of Preparation Examples 2-1 to 2-12 and Comparative Preparation Example 2-1 were performed in the same manner as in Experimental Example 1, and the results were It is shown in Table 8 below.

division Mo precursor
compound Resistivity value
(Ω·cm) Thin film deposition rate (Å/cycle) Impurity concentration Carbon (at%) Manufacturing Example 2-1 Example 2-1 (1.1 ~ 1.3)×10 ^-3 1.14 ~ 1.16 10.1 ~ 11.0 Manufacturing Example 2-2 Example 2-2 (1.4 ~ 1.6)×10 ^-3 1.15 ~ 1.17 9.8 ~ 10.1 Preparation Example 2-3 Example 2-3 (1.3 ~ 1.5)×10 ^-3 1.13 ~ 1.18 9.5 ~ 9.9 Manufacturing Example 2-4 Example 2-4 (1.7 ~ 1.8)×10 ^-3 1.07 ~ 1.12 10.9 ~ 11.0 Manufacturing Example 2-5 Example 2-5 (1.4 ~ 1.5)×10 ^-3 1.05 ~ 1.09 10.1 ~ 10.9 Preparation Example 2-6 Example 2-6 (1.6 ~ 1.7)×10 ^-3 1.02 ~ 1.05 10.2 ~ 10.4 Manufacturing Example 2-7 Example 2-7 (1.5 ~ 1.6)×10 ^-3 1.06 ~ 1.12 9.8 ~ 9.9 Manufacturing Example 2-8 Example 2-8 (1.6 ~ 1.7)×10 ^-3 1.11 ~ 1.15 9.0 ~ 9.5 Manufacturing Example 2-9 Example 2-9 (1.4 ~ 1.5)×10 ^-3 1.12 ~ 1.15 10.2 ~ 10.4 Preparation Example 2-10 Example 2-10 (1.3 ~ 1.4)×10 ^-3 1.25 ~ 1.27 11.2 to 11.1 Manufacturing Example 2-11 Example 2-11 (1.4 ~ 1.6)×10 ^-3 1.05 ~ 1.10 4.5 ~ 5.5 Preparation Example 2-12 Example 2-12 (1.4 ~ 1.5)×10 ^-3 1.04 ~ 1.10 5.5 to 6.0 Comparative Production Example 2-1 Comparative Example 2-1 (1.0 ~ 1.5)×10 ^-3 0.85 ~ 0.98 11.5 ~ 12.0

According to Table 8, the thin film deposition rates of thin films prepared by using the molybdenum compound as a precursor among the organometallic compounds of the present invention all exceed 1.00 Å/cycle, preferably 1.00 to 1.50 Å/cycle, more preferably 1.05. It was confirmed to have an excellent thin film deposition rate by satisfying ~ 1.35 Å/cycle. Then, the specific resistance value 2.5ⅹ10 ^-3 Ω · ㎝, preferably less than ^{1.0 × 10 -3 ~ 2.2 × 10} -3 Ω · ㎝, more preferably from ^{1.0 × 10 -3 ~ 1.9 × 10} -3 Ω · ㎝ It was confirmed that the specific resistance value was relatively lower than that of the tungsten compound precursor, and it was confirmed that molybdenum has relatively better electrical properties than tungsten.

Through the above Examples and Experimental Examples, it was confirmed that an organometallic and/or metal-containing thin film having excellent physical properties (low specific resistance, high thin film deposition rate, low impurity content) can be formed by using the organometallic precursor compound of the present invention. Could.

Claims (11)

For forming a thin film for semiconductors represented by the following formula (1) Organometallic precursor compound.
[Formula 1]

In Formula 1, M is molybdenum (Mo),
When X is N, R ₁ is -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, R ₂ is a straight-chain alkyl group of _{C 1 to 3 , and R 3} and R ₄ are -C(CH ₃ ) ₃ ; Or
When X is N, R ₁ is -CH ₂ CH ₂ -, R ₂ is a C _1-3 linear alkyl group, and R ₃ and R ₄ are -C(CH ₃ ) ₃ ; Is,
X is the number of persons (P), the arsenic (As), or

When, R ₁ is -CH ₂ CH ₂ -, R ₂ is a C _1-3 linear alkyl group, and R ₃ and R ₄ are -C(CH ₃ ) ₃ ;
delete delete delete An organometallic precursor compound for forming a thin film for semiconductors represented by the following Chemical Formula 1.
[Formula 1]

In Formula 1, M is tungsten (W),
When X is N, R ₁ is -CH ₂ CH ₂ -and R ₂ is -CH ₃ , and R ₃ and R ₄ are -CH ₂ CH ₃ , -C(CH ₃ )(CH ₂ CH ₃ ) ₂ or -C(CH ₃ ) ₃ ; Or
When X is N, R ₁ is -CH ₂ CH ₂ OCH ₂ -, R ₂ is a C _1-3 linear alkyl group, and R ₃ and R ₄ are -C(CH ₃ ) ₃ ; ego,
X is the number of persons (P), the arsenic (As), or

When, R ₁ is -CH ₂ CH ₂ -, R ₂ is a C _1-3 linear alkyl group, R ₃ and R ₄ are -C(CH ₃ ) ₃ ; to be.
delete delete delete delete delete A thin film comprising an organometallic deposition layer or a metal deposition layer formed by using the organometallic precursor compound of claim 1 or 5 as a precursor.

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