KR20200041247A - A organic-metal precirsor compound and othin film prepared by using the same - Google Patents

Abstract

An organometallic precursor compound and an organometallic thin film manufacturing method using the same of the present invention satisfy high volatility and excellent chemical and thermal stability, and at the same time have a significantly improved thin film deposition rate even at low temperatures. In addition, by providing the organometallic precursor compound which can be used to form a dielectric thin film in a semiconductor device, it is possible to manufacture an organic metal-containing and/or metal-containing thin film having alleviated property 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 thin film prepared using the same, and more specifically, an organometallic precursor compound that satisfies excellent chemical and thermal stability and is capable of easily depositing a thin film even at a low temperature. It relates to an organic metal deposited layer or a thin film comprising a metal deposited layer.

Chemical vapor deposition (CVD) and atomic layer deposition (ALD) allow thin films for semiconductor devices to be formed as 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 the chemical reaction of a metal-organic compound (precursor), it is important to develop an optimum precursor by predicting its properties and reaction process. Therefore, efficient precursor development has been continued to obtain specific properties for specific types of thin films.

Precursors are molecules for CVD and ALD processes, and some of their inherent 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 in storage conditions and transport conditions, and gas-phase thermal stability is also required to prevent the inflow of impurities into 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 to be considered for precursors in the precursor design stage is the removal of impurities from the ligands from the thin film during the deposition process.

Tungsten is used in a variety of applications useful for the fabrication of nano-devices. Deposition of pure tungsten can be used to fill the holes (“contact holes”) making 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, in order to protect the underlying Si by the penetration with fluorine, or to ensure the adhesion of tungsten to silicon dioxide.

Tungsten-silicide can be used to increase the conductivity of the gate line on top of the polysilicon gate 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 a silicon source because it allows higher deposition temperatures, resulting in lower fluorine concentrations in the deposited thin films. .

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

Since WF ₆ is a liquid and highly volatile, +6 of W is oxidized, H ₂ can be used for deposition of pure tungsten thin film in CVD mode using H ₂ at high temperature. In addition, WF ₆ can be used in CVD mode in combination with silane for the production of tungsten silicide thin films at low temperatures. However, WF ₆ is limited due to the high thermal budget required for the deposition of pure tungsten thin films or due to the fluorine that causes etching of the underlying silicon surface.

Because of the zero oxidation state of W in W (CO) ₆ , it can be used to deposit pure tungsten or tungsten nitride thin films in CVD mode. However, due to the high toxicity of the material, it was limited to mass production.

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

However, in the bis cyclopentadienyl tungsten precursor having the formula W (RCp) ₂ H ₂ , the +6 oxidized state of W can be used in CVD mode for deposition of pure tungsten, but requires high deposition temperature, resulting in carbon contamination do.

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

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

U.S. Pat.No. 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 the disadvantage that carbon can be introduced in the resulting thin film. Tungsten molecules can contain several types of ligands that are not homologous. Therefore, their synthesis is done in several stages, and the complexity and difficulty of the synthesis will eventually increase the cost.

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

That is, depositing a tungsten-containing thin film (pure tungsten, tungsten nitride or tungsten silicide) in a CVD or ALD mode could be a problem of high C, O or F content in the thin film. Accordingly, a tungsten precursor compound having high volatility and passion stability, satisfactory reactivity in the deposition process, and easy deposition even at low temperatures is needed to produce a pure tungsten-containing thin film with little impurities.

US Patent Publication No. US 2006-0125099 A1 (published on June 15, 2006)

The present invention has been devised to solve the above-mentioned problems, and the problem to be solved by the present invention is to use a organometallic precursor compound that satisfies high volatility, excellent chemical and thermal stability, and is capable of easily depositing thin films even at low temperatures. It is an object to provide a thin film comprising the prepared organic metal deposition layer or a metal deposition layer.

The present invention provides an organometallic precursor compound represented by the following Chemical Formula 1 to solve the above-mentioned 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, 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, X is a nitrogen atom (N), a number of atoms (P), a non-atomic 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 _1-3 alkyl group, and R ₃ and R ₄ may each independently be a C _1-5 alkyl group.

In addition, the present invention provides an organometallic precursor compound represented by Formula 2 below.

[Formula 2]

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

According to a preferred embodiment of the present invention, R ₁ ′ is a C _1-2 alkyl group or heteroalkyl group, R ₂ is a C _1-3 alkyl group, R ₃ and R ₄ are each independently C _1-5 It may be an alkyl group.

In addition, the present invention provides an organometallic precursor compound represented by Formula 3 below.

[Formula 3]

In Chemical 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.

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

[Formula 4]

In Chemical 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 by being represented by the following formula (5).

[Formula 5]

In Chemical 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 characterized in that any one of the organometallic precursor compounds is for the production of thin films containing organometallic materials for semiconductors.

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

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

The term “alkyl” refers to an aliphatic hydrocarbon group. The alkyl moiety may be a "saturated alkyl" group, meaning that it does not contain any alkene or alkyne moiety. The alkyl site may be a "unsaturated alkyl" site, which means that it contains at least one alkene or alkyne site. The alkyl moiety, whether saturated or unsaturated, can be branched, straight chain, or cyclic. In addition, alkyl includes both "substituted or unsubstituted alkyl".

The term "substituted or unsubstituted" means that both the substituted and unsubstituted substituents are substituted unless otherwise specified, and when substituted, the substituents are alkyl, acyl, cycloalkyl (dicyclealkyl and tri Cycloalkyl), perhaloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, azide, amine, ketone, ether, amide, ester, triazole, isocyanate, arylalkyloxy, aryloxy, Merpento, 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, ah , Amino, amido, nitro, ether, ester, halogen, thiol, aldehyde, carbonyl, phosphorus, sulfur, phosphate, phosphat, phosphite, sulfate, disulfide, oxy, mercapto and hydrocarbylmono- and Amino, including di-substituted amino groups, and their derivatives, individually and independently selected from one or more groups, including, but not limited to, substituted by various substituents commonly used in the art. It is meant to include a comprehensive case. 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 one or more of the carbon atoms of the 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 have high volatility, excellent chemical and thermal stability, and at the same time 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, a thin film including an organometallic deposition layer or a metal deposition layer having improved characteristics due to by-products can be manufactured.

1 and 2 are each 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 the tungsten precursor compound synthesized in Example 1-1.
4 is a graph of measuring resistivity and deposition rate according to RF voltage intensity of the ALD-deposited tungsten thin film of Preparation Example 1-1.
5 is a graph of measuring resistivity and deposition rate 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, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily practice. However, the examples are not intended to limit the scope of the present invention, which should be interpreted as to aid understanding of the present invention.

As described above, the conventional organometallic precursor compound was limited in the semiconductor mass production process due to the low film deposition rate, and due to the low chemical and thermal stability, the stepped coatability due to the decomposition of the precursor at a high substrate temperature during deposition due to low chemical and thermal stability. There is a problem that the characteristics are lowered due to degradation, by-products of the process and the deposited thin film, and the reliability and efficiency of the process are low.

Accordingly, the present invention seeks to solve the above-mentioned problem by providing an organometallic precursor compound represented by the following Chemical Formula 1. Through this, it is possible to provide an organometallic precursor compound having an effect of satisfying high volatility, excellent chemical and thermal stability, and having a significantly 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 comprising an organic metal deposition layer or a metal deposition layer with improved characteristic degradation 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 _2-10 alkylene group or a heteroalkylene group, R ₂ is a C _1-5 Alkylene group or heteroalkylene group, R ₃ and R ₄ are each independently a C _1-10 alkyl group, X is a nitrogen atom (N), phosphorus atom (P), arsenic atom (As) or

to be.

As described above, the organometallic precursor compound according to the present invention has a structure to form a ring with cyclopentadiene (Cp, cyclopentadiene), M, R ₁ and X, and through the formation of such a ring structure, thin film deposition is significantly improved even at low temperatures. It is possible to provide a tungsten precursor having a velocity. In addition, an organic metal-containing thin film having improved characteristics due to by-products can be manufactured using the organometallic precursor compound.

이며, 바람직하게는 N, P 또는

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

Is, preferably N, P or

It may be, and more preferably N.

In addition, R ₁ of Chemical Formula 1 is a C _2-10 alkylene group or a heteroalkylene group, preferably a C _2-5 alkylene group, more preferably a C _2-3 alkylene group, , Most preferably-(CH ₂ )-. Through this, it is possible to provide a high-purity organic metal-containing thin film with improved characteristics 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 due to by-products may occur.

Formula wherein R ₁ is an alkyl group or a heteroalkyl of C _2-10 1 alkylene rep means is, R ₁ is the number of carbon atoms is 2 to 10 private substituted or unsubstituted alkylene group or a carbon number of 2 to 10 private substituted or unsubstituted heteroaryl It means 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 that the number of carbon atoms excluding the hetero atom is 2-10.

The hetero atom in the heteroalkylene group can be widely selected as long as it is an atom that can form a stable substituent by combining with a carbon atom in the alkyl group, but preferably a nitrogen atom (N), oxygen atom (O) or sulfur atom ( S).

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

In addition, R ₂ of Formula 1 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 more preferably May be -CH ₃ .

The meaning of R ₂ is 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 that the number of carbon atoms excluding heteroatoms is 1-5.

Among the heteroalkyl groups of R ₂ , heteroatoms can be generally selected as long as they are atoms capable of forming a stable substituent by bonding with carbon atoms in the alkyl group, but preferably nitrogen atom (N), oxygen atom (O) or sulfur It may be an atom (S).

In addition, the number of hetero atoms in the heteroalkyl group of R ₂ is not limited as long as it is capable of forming a stable organometallic compound while containing 1 to 5 carbons, preferably 1 to 3, It may be more preferably 1 to 2, and even more preferably 1.

Meanwhile, R ₃ and R ₄ in Chemical Formula 1 are each independently a C _1-10 alkyl group, and preferably each independently a C _1-5 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 It may be preferably tC ₄ H ₉ .

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

Hereinafter, it will be described in detail except for overlapping contents.

In addition, the present invention provides an organometallic precursor compound represented by Formula 2 below. Through this, a high purity thin film can be deposited, thereby obtaining a thin film with improved characteristics due to by-products.  

[Formula 2]

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

The R ₁ ′ of Formula 2 is a C _1-4 alkylene group or a heteroalkylene group, preferably a C _1-3 alkylene group, and more preferably a C _1-2 alkylene group or heteroalkylene. Group, and most preferably-(CH ₂ )-.

The meaning of R ₁ ′ is a C _1-4 alkylene group or 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 Rengi. More specifically, the meaning of a C _1-4 heteroalkylene group does not mean that the total number of carbon and heteroatoms is 1-4, but that the number of carbon atoms excluding the hetero atom is 1-4.

Likewise, the meaning of R ₁ ′ is a C _1-2 alkylene group or heteroalkylene group, R ₁ ′ is a substituted or unsubstituted alkylene group having 1 to 2 carbon atoms, or a substituted or unsubstituted hetero atom having 1 to 2 carbon atoms. It means an alkylene group. In addition, the meaning of the C _{1 ~ 2} heteroalkylene group does not mean that the total number of carbon and heteroatoms is 1 to 2, but that the number of carbon atoms excluding the hetero atom is 1 to 2 carbon atoms.

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

Further, the number of hetero atoms in the heteroalkylene group is not limited as long as it can form a stable organometallic compound while containing 1 to 4 carbons, but may preferably be 1 to 6, and more preferably It may be 1 to 3 crabs, and more preferably 1 to 2 crabs.

In addition, R ₂ of 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 .

Means that the R ₂ of formula (II) of the alkyl group or heterocyclic group of C _1-5, means that R ₂ has a carbon number of 1-5 individual substituted or unsubstituted alkyl group or a carbon number of 1-5 individual substituted or unsubstituted heteroaryl group . 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 that the number of carbon atoms excluding the hetero atom is 1-5.

The hetero atom in the heteroalkyl group of Formula 2 may be widely selected as long as it is an atom that can form a stable substituent by combining with a carbon atom in the alkyl group, but may preferably be N, O or S.

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

Meanwhile, R ₃ and R ₄ in Chemical Formula 2 are each independently 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 tC ₄ H ₉ .

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

In addition, the present invention provides an organometallic precursor compound represented by Formula 3 below. Through this, it is possible to provide an organometallic precursor compound having an effect of satisfying high volatility, excellent chemical and thermal stability, and having a significantly improved thin film deposition rate even at a low temperature. In addition, there is an advantage that can provide a tungsten-containing thin film with improved characteristics due to by-products.

[Formula 3]

In Chemical 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 _1-3 alkyl group, and R ₃ and R ₄ are each independently a C _1-5 alkyl group.

The R ₂ of Formula 3 is a C _1-3 alkyl group, preferably a C _1-2 alkyl group, and more preferably CH ₃ .

In addition, R ₃ and R ₄ in Chemical Formula 3 are each independently a C _1-5 alkyl group, and preferably each independently may be a C _1-4 alkyl group, -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 tC ₄ H ₉ .

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

[Formula 4]

In Chemical 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.

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

[Formula 5]

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

In addition, the organometallic precursor compound can be widely used as long as it is a field in which it can be commonly used, but is preferably included or used in the process of manufacturing a semiconductor material in the semiconductor field. In addition, more preferably, it can be used for the production of thin films containing organic metal for semiconductors.

Specifically, the organometallic precursor compounds may be used as precursors for forming thin films included in semiconductors. Precursor refers to a material prior to becoming a specific material in metabolism or reaction, and may form a thin film used in semiconductors by physically / chemically adsorbing 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 low-by-product or high-purity tungsten, chromium or molybdenum without by-products, thereby improving the deterioration of properties due to by-products.

Specifically, when the organometallic thin film containing the organometallic precursor compound of the present invention is prepared 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 shape may be modified during the process. have. That is, the final shape may be various when the thin film included in the semiconductor is manufactured by using the organometallic precursor compound of the present invention as a precursor.

 Furthermore, the present invention comprises the steps of: a) providing a vapor comprising any one of the organometallic precursor compounds above, and b) reacting the vapor with a substrate according to a deposition method, thereby containing an organometallic-on at least one side of the substrate. An organic metal-containing thin film production method comprising 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 time of forming the substrate, and the process speed can be shortened by increasing the film deposition rate. In addition, it can be used in a wide temperature range while reducing the contamination in the process, it is possible to significantly improve the reliability and efficiency of the manufacturing process. Furthermore, through the above-described manufacturing method, it is possible to obtain a thin film having improved characteristics due to by-products, excellent uniformity, and improved step coating properties.

Hereinafter, a description will be given in detail, excluding the contents overlapping with the above-described contents.

First, a) the step of providing a vapor containing any one of the organometallic precursor compounds described above 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 at which the metal source can be obtained with sufficient vapor pressure. The carrier gas can be selected from Ar, He, H ₂ , N ₂ or mixtures thereof. The metal source can be mixed in a container with a solvent or another metal source or mixtures thereof. The vessel may be preferably heated at a temperature ranging from 25 ° C to 200 ° C, and the temperature of the container may be adjusted to control the amount of precursor evaporated. The pressure in the vessel can be changed to control the evaporation level 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 can vary from 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 or may not be mixed with a solvent. Also, the metal source can be mixed with another metal source. The mixture of metal sources can be mixed with a solvent or a solvent mixture. The metal source can be mixed with a stabilizer. Such solvents include 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 Dimethyl sulfoxide, oxygen-containing solvents such as tetrahydrofuran, dioxane. Meanwhile, the concentration of the mixed solution containing the solvent may preferably include 50 to 99.9% by weight of the metal source.

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

The source of vaporized metal is introduced into the 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 a 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, more preferably 450 ° C or less. Meanwhile, the process may be assisted by a non-limitingly selected plasma technique to improve the reactivity of the vaporized metal source and / or the reactivity of other gas species used in the process.

On the other hand, 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, preferably chemical vapor phase Chemical vapor deposition (CVD) or atomic layer deposition (ALD) may be used.

First, atomic layer deposition (ALD) is a method of growing a thin film by cross-injecting a raw material containing metal and a reaction gas (for example, NH _3, etc.), and reacting the raw material and gas to grow the atomic unit thin film. This is a method of repeatedly controlling the thickness of the thin film. Specifically, the organometallic precursor compound according to the present invention may be delivered to the chamber in a vapor phase after the precursor is injected into the vaporizer. 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 transporting volatile gas using vapor pressure, a direct liquid injection method, or a liquid delivery method in which the precursor material is dissolved in an organic solvent and transferred (Liquid Delivery System; LDS) Can be used. In this case, one or more inert gases selected from Ar, N ₂ , He, or H ₂ may be used as a transport gas or a diluent gas for moving the precursor material on the substrate, and more preferably from Ar or N ₂ Can be selected. Meanwhile, the N ₂ canister flow rate 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 on the substrate, and the unadsorbed precursor material may be purged. Inert gas may be used as the purge gas. Next, a reactant can be supplied. The reactant may include oxidizing agents such as H ₂ O, H ₂ O ₂ , O ₂ , O ₃ , and N ₂ O. An organic metal and / or metal-containing thin film may be formed by reacting the reactant and the precursor material, and the thin film may include tungsten, chromium, or molybdenum. Next, the unreacted material is purged. Accordingly, excess reactants and generated by-products can be removed.

On the other hand, the precursor material supply step, purge (purge), reactant supply step and purge (purge) is a unit cycle. The unit cycle can be repeated to form a thin film of a desired thickness. Preferably, 10 to 10,000 cycles may be repeated.

In addition, when using the atomic layer deposition method, the temperature may be preferably 100 ℃ ~ 450 ℃, more preferably 150 ℃ ~ 350 ℃ range. 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. In addition, the resistivity is less than 3.0ⅹ10 ^-3 Ω · cm, preferably 1.9 × 10 ^-3 ~ 2.9 × 10 ^-3 Ω · cm, more preferably 2.0 × 10 ^-3 ~ 2.4 × 10 ^-3 Ω · cm can be satisfied. Further, it is possible to provide a high purity ALD deposited thin film by including impurity carbon (C) at 12.5 at% or less, preferably 11.0 at% or less, and more preferably 7.0 at%.

Next, the chemical vapor deposition method (CVD) supplies gas containing elements constituting the thin film material to be formed on the substrate, thereby performing the substrate through chemical reactions such as thermal decomposition, photolysis, redox reaction, and substitution on the substrate surface. It is a method of forming a thin film on the surface. When the chemical vapor deposition method is used, the temperature may be preferably 100 ° C to 700 ° C, and more preferably 200 ° C to 500 ° C. Further, the pressure may be preferably 0.01 Torr to 800 Torr, and more preferably 1 Torr to 200 Torr. In addition, the carrier gas may preferably be N ₂ , He, Ar, H ₂ , and more preferably Ar or N ₂ . The 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, saturated or unsaturated hydrocarbons, cyclic ethers, acyclic ethers, esters, alcohols, cyclic amines, acyclic A composition containing a residual amount of one or more organic compounds selected from amines, cyclic sulfides, non-cyclic sulfides, phosphines, beta-dikytones, and beta-chitoesters, and a metal-containing thin film using the same How to do.

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

After all, the present invention provides an organometallic precursor compound and a thin film prepared using the same, 1) not only can increase the reliability and efficiency of the manufacturing process, but 2) satisfies the improved chemical and thermal stability, and 3) this At the same time, it is possible to achieve significantly improved thin film deposition rates even at low temperatures. In addition, the excellent organometallic precursor compound as described above can be used for the production of thin films for semiconductors, thereby improving the characteristics of the product due to by-products, having excellent step coverage, and having a high dielectric constant, which is an equivalent electrical oxide film. It is possible to provide an organic metal-containing and / or metal-containing thin film for semiconductors having a thickness (EOT) and physically without tunneling, and a semiconductor structure including the same.

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

[Example]

Example 1-1: Tungsten (W) precursor compound synthesis

The reactions of the following steps (1), (2) and (3) were sequentially performed to prepare compounds represented by the following Chemical Formula 1-1.

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

After adding 100 g (0.252 mol, 1.00 equivalent) of WCl ₆ to a 2 L Schlenk flask containing 500 ml of toluene and cooling to -50 ° C or less while stirring, n-tert-butyl trimethylsilyl amine (n-tert-butyl trimethylsilyl amine) 146.5 g (1.008 mol, 4.00 eq) 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. 100 g (yield: 84%) of the first stage product was obtained.

(2) Step 2 (Synthesis of (t-bytyl-N =) ₂ W (NMe ₂ ) ₂ ): 100 g (0.213) of (t-bytyl-N =) ₂ WCl _{2 in a 2} L Schlenk flask containing 500 ml of hexane mol, 1.00 equiv.) and cooled to below -50 ° C while stirring, and then 27.1 g (0.531 mol, 2.50 equiv) of Li (AMD) was added for 1 hour. The reaction was terminated by stirring the mixed reaction solution at room temperature for 3 hours. 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 obtain 36 g of a red liquid compound (yield: 38%).

(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 500 ml of hexane ₂ ) ₂ 36 g (0.087 mol, 1.00 eq) was added and cooled to -50 ° C. while stirring, and cyclopentadienylethylmethylamine (CpCH ₂ CH ₂ NCH ₃ ) was added for 1 hour. The reaction was terminated by stirring the mixed reaction solution at room temperature for 5 hours. Subsequently, after completely removing the solvent under reduced pressure, the resulting liquid is distilled under reduced pressure (boiling point: 100 ° C., 0.2 torr) to produce 25 g of tungsten precursor compound (CEMAW), which is a compound represented by the following Chemical Formula 1-1, which is a yellow liquid. (Yield 64%).

And, the results of ¹ H NMR and ¹³ C NMR analysis of the prepared CEMAW are shown in FIGS. 1 ( ¹ H NMR) and 2 ( ¹³ C NMR), respectively.

In addition, the results of TGA analysis on the prepared compounds are 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 Formula 1 and having X, R ₁ , R ₂ , R ₃ and R ₄ 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

Compound represented by the formula (6) was synthesized.

[Formula 6]

Comparative Example 1-2

Compound represented by the formula (7) was synthesized.

[Formula 7]

Preparation Example 1-1: Tungsten thin film formation 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 using CEMAW as a cycle for supplying the precursor on the substrate-1st purge-reactant supply step-2nd purging are shown in Table 4 below.

division Condition ALD deposition equipment PEALD (Isaac 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
* Reaction material (NH ₃ ) supply time: 3 seconds
* 2nd purge time: 3 seconds to 10 seconds Cycle number 500 cycles RF voltage (Power) strength 300 ~ 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: normal temperature (LDS)
* Vaporizer: 140 ℃
* Transfer line: 140 ℃

Experimental Example 1: Analysis of resistivity, deposition rate, and EDS 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 specific resistance and deposition rate according to RF voltage are shown in FIG. 4. In this case, the measurement value of FIG. 4 is measured when the cycle time is tungsten precursor supply / primary purge / reactant supply / secondary purge time is 3 seconds / 5 seconds / 3 seconds / 5 seconds. And, when the RF voltage strength of 700W, the specific resistance and deposition rate measurement values according to the change in purge time are shown in FIG. In addition, when the tungsten precursor supply / 1st purge / reactant supply / 2nd purge time is 3 sec / 5 sec / 3 sec / 5 sec, EDS measurement results according to RF voltage intensity are shown in FIG. 6.

Looking at Figure 4, as the RF voltage intensity increases, the thin film deposition rate tends to decrease, and when the resistivity is 300 W, the highest, the lowest at 500 W, and after 500 W, the resistivity increases again. You can. That is, the RF voltage strength of 400W to 750W, preferably 450W to 600W, which satisfies the specific resistance value of 3.0ⅹ10 ^-3 Ω · cm or less, preferably 2.0 × 10 ^-3 to 2.9 × 10 ^-3 Ω · cm, is appropriate. Can be confirmed.

And, looking at Figure 5, when the RF voltage strength of 700W, as the purge time increases, it can be confirmed that the resistivity and the thin film deposition rate decreases and then increases again, and the appropriate purge time is preferably 3 to 6 seconds, or 8 Seconds are preferably 10 seconds, and considering economics, 3 to 6 seconds will be more preferable.

In addition, referring to FIG. 6, it can be seen that as the RF voltage intensity increased, the impurities tended to decrease in the content of carbon (C) and nitrogen (N), and the concentration of carbon as an impurity in the thin film was 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 is not broken, but is firmly bonded.

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

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

In the same manner as in Preparation Example 1-1, a tungsten thin film was formed through an ALD deposition process, and the RF voltage was applied using the tungsten compounds of Examples 1-2 to 1-16 and Comparative Examples 1-1 to 1-2, respectively. The intensity of 500 W, CEMAW was performed on the substrate by performing 500 cycles of the precursor supply step-1st purge-reactant supply step-2nd purge at 3 sec / 5 sec / 3 sec / 5 sec 1 cycle to form a tungsten thin film. .

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

The 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 Specific resistance value (Ω · ㎝) Thin film deposition rate (Å / cycle) Impurity concentration Carbon (at%) Preparation 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 Preparation Example 1-3 (2.3 ~ 2.4) × 10 ^-3 1.05 ~ 1.10 11.5 ~ 12.0 Preparation Example 1-4 (2.7 ~ 2.8) × 10 ^-3 0.95 ~ 1.00 8.8 ~ 9.3 Preparation Example 1-5 (2.4 ~ 2.5) × 10 ^-3 1.00 ~ 1.05 9.0 ~ 9.5 Preparation Example 1-6 (2.5 ~ 2.6) × 10 ^-3 1.05 ~ 1.10 10.8 ~ 11.3 Preparation Example 1-7 (2.5 ~ 2.6) × 10 ^-3 0.90 ~ 0.95 10.5 ~ 11.0 Preparation Example 1-8 (2.6 ~ 2.7) × 10 ^-3 0.85 ~ 0.90 10.9 ~ 11.4 Preparation 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 Preparation 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 ~ 1.05 11.0 ~ 11.5 Preparation Example 1-13 (1.9 ~ 2.0) × 10 ^-3 1.30 ~ 1.35 5.5 ~ 6.0 Preparation Example 1-14 (2.1 ~ 2.2) × 10 ^-3 1.25 ~ 1.30 5.5 ~ 6.0 Preparation Example 1-15 (2.2 ~ 2.3) × 10 ^-3 1.10 ~ 1.15 8.5 ~ 9.0 Preparation 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 ~ 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

Through the Table 5, the thin film deposition rate of the thin film prepared using the tungsten compound as a precursor among the organometallic compounds of the present invention exceeds 0.7 Å / cycle, preferably 0.95 to 1.5 Å / cycle, preferably 1.05 to It can be confirmed that it has an excellent thin film deposition rate by satisfying 1.55Å / cycle, and the specific resistance value is less than 3.0ⅹ10 ^-3 Ω · cm, preferably 1.9 × 10 ^-3 ~ 2.9 × 10 ^-3 Ω · cm, more preferably It can be seen that satisfies 2.0 × 10 ^-3 to 2.4 × 10 ^-3 Ω · cm.

Furthermore, even in the case of thin film purity, all of the carbon that is a contaminant source is 12.5 at% or less, preferably 11.0 at% or less, and through this, the amount of impurities remaining in the present invention is remarkably low, thereby providing a thin film with improved purity. Able to know.

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

Example 2-1: Molybdenum (Mo) precursor compound synthesis

The reactions of the following steps (1), (2) and (3) were sequentially performed to prepare compounds represented by the following Chemical Formula 2-1.

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

In a 2L Schlenk flask, MoO ₂ Cl ₂ (25 g) was fractionated and acetonitrile was added. After stirring, t-butyl isocyanate ( tert -Butyl Isocyanate) was added dropwise. Next, after stirring at room temperature, the mixture was refluxed for 12 hours. Next, the solvent t was stripped and then recrystallized to turn on. (+ N =) 37 g of ₂ MoCl ₂ was synthesized (yield: 93%).

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

After adding (+ N =) ₂ MoCl ₂ (1.00 eq.) To a 2L Schlenk flask containing 500 ml of hexane and cooling to -50 ° C or less while stirring, Li (AMD) (2.50 eq.) Was slowly added for 1 hour. Did. Next, the reaction was terminated by stirring it at room temperature for 3 hours. The resulting solid (LiCl) was filtered, 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 500 ml of hexane, (+ N =) ₂ Mo (NMe ₂ ) ₂ (1.00 equivalent) synthesized in step ₂ was added and cooled to -50 ° C with stirring, followed by cyclopentadienylethylmethylamine (CpCH ₂ CH ₂ NCH ₃ ) was slowly added for 1 hour. Next, the reaction was terminated by stirring it at room temperature for 5 hours. Subsequently, after completely removing the solvent under reduced pressure, the resulting liquid is distilled under reduced pressure (boiling point: 100 ° C., 0.1 torr) to yield 20 g of a molybdenum precursor compound, a compound represented by the following Chemical Formula 1-2, which is a dark yellow liquid. 60%).

And, 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 a structure of Formula 2-1 and X, R ₁ , R ₂ , R ₃ and R ₄ 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

Compound represented by the formula (8) was synthesized.

[Formula 8]

Production Example 2-1 to 2-12 and Comparative Production Example 2-1

Each of the molybdenum (Mo) precursor compounds of Examples 2-1 to 2-12 and Comparative Example 2-1 was formed with a molybdenum thin film using atomic layer deposition (ALD) under the same conditions and methods as those of Preparation Example 1-1, Preparation Examples 2-1 to 2-12 and Comparative Production Example 2-1 were performed, respectively. At this time, during deposition, ALD deposition conditions of one cycle are shown in Table 4 above.

Experimental Example 3: Analysis of resistivity, deposition rate and EDS of ALD-deposited tungsten thin film

The 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 Production Example 2-1 were performed in the same manner as in Experimental Example 1, and the results were obtained. It is shown in Table 8 below.

division Mo precursor
compound Specific resistance value
(Ω · cm) Thin film deposition rate (Å / cycle) Impurity concentration Carbon (at%) Preparation Example 2-1 Example 2-1 (1.1 ~ 1.3) × 10 ^-3 1.14 ~ 1.16 10.1 ~ 11.0 Preparation 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 Preparation Example 2-4 Example 2-4 (1.7 ~ 1.8) × 10 ^-3 1.07 ~ 1.12 10.9 ~ 11.0 Preparation 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 Production Example 2-7 Example 2-7 (1.5 ~ 1.6) × 10 ^-3 1.06 ~ 1.12 9.8 ~ 9.9 Preparation Example 2-8 Example 2-8 (1.6 ~ 1.7) × 10 ^-3 1.11 ~ 1.15 9.0 ~ 9.5 Preparation 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 ~ 11.1 Production 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 ~ 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

Through the Table 8, the thin film deposition rate of the thin film prepared by using the molybdenum compound as a precursor among the organometallic compounds of the present invention exceeds 1.00 Å / cycle, preferably 1.00 to 1.50 Å / cycle, more preferably 1.05 It was confirmed that it has an excellent thin film deposition rate by satisfying ~ 1.35 Å / cycle. And, the specific resistance value is less than 2.5ⅹ10 ^-3 Ω · cm, preferably 1.0 × 10 ^-3 to 2.2 × 10 ^-3 Ω · cm, more preferably 1.0 × 10 ^-3 to 1.9 × 10 ^-3 Ω · cm It could be confirmed that, the specific resistance value is a relatively low specific resistance value than the tungsten compound precursor, it was confirmed that the molybdenum is relatively good electrical properties than tungsten.

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

Claims (11)

An organometallic precursor compound represented by Formula 1 below.
[Formula 1]

In Chemical Formula 1, M is tungsten (W), chromium (Cr) or molybdenum (Mo), R ₁ is C _2-10 alkylene group or heteroalkylene group, R ₂ is C _1-5 alkyl group or hetero Alkyl group, R ₃ and R ₄ are each independently a C _1-10 alkyl group, X is a nitrogen atom (N), personnel (P), non-atom (As) or

to be.
According to claim 1,
The X is an organometallic precursor compound, characterized in that N.
According to claim 1,
The R ₁ is an organometallic precursor compound, characterized in that it is a C _2-5 alkylene group.
According to claim 1,
The R ₂ is an alkyl group of C _{1 ~ 3} , R ₃ and R ₄ are each independently an organometallic precursor compound, characterized in that C _{1 ~ 5} alkyl group.
An organometallic precursor compound represented by the following Chemical Formula 2.
[Formula 2]

In Chemical Formula 2, M is tungsten (W), chromium (Cr) or molybdenum (Mo), R ₁ ′ is a C _1-4 alkylene group or a heteroalkylene group, R ₂ is a C _1-5 alkyl group, or Heteroalkyl group, R ₃ and R ₄ are each independently a C _1-10 alkyl group.
The method of claim 5,
The R ₁ 'is a C _{1 ~ 2} alkylene group or heteroalkylene group, R ₂ is a C _{1 ~ 3} alkyl group, R ₃ and R ₄ are each independently C _{1 ~ 5} alkyl group characterized in that the organic Metal precursor compound.
An organometallic precursor compound represented by Formula 3 below.
[Formula 3]

In Chemical Formula 3, M is tungsten (W), chromium (Cr), or molybdenum (Mo), R ₂ is a C _1-3 alkyl group, and R ₃ and R ₄ are each independently a C _1-5 alkyl group. .
The organometallic precursor compound according to claim 7, wherein the tungsten precursor compound represented by Chemical Formula 3 is represented by the following Chemical Formula 4.
[Formula 4]

In Chemical Formula 4, M is tungsten (W), chromium (Cr), or molybdenum (Mo), and R ₃ and R ₄ are each independently a C _3-5 alkyl group.
Organometallic precursor compound, characterized in that represented by the formula (5).
[Formula 5]

In Chemical Formula 5, M is tungsten (W), chromium (Cr), or molybdenum (Mo).
The organometallic precursor compound according to any one of claims 1 to 9, wherein the organometallic precursor compound is for manufacturing thin films for semiconductors.
A thin film comprising an organometallic deposition layer or a metal deposition layer prepared by using the organometallic precursor compound of any one of claims 1 to 9.

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