KR20230009325A - Molybdenum precursor compound, method for preparing the same, and method for depositing molybdenum-containing thin film using the same - Google Patents

Abstract

The present invention relates to a molybdenum precursor compound, a manufacturing method thereof, a precursor composition for depositing a thin film having the compound, a molybdenum-containing thin film using the compound, and a deposition method of the thin film. The molybdenum precursor compound has excellent thermal stability and low specific resistance, easily controls a deposition rate to control desired thickness and composition of the thin film when depositing the molybdenum-containing thin film, and forms excellent coverage and the uniform thin film even on a substrate with a pattern (a groove) on a surface, a porous substrate, a plastic substrate or a substrate with a complex shape, so that high-quality molybdenum-containing thin film can be realized.

Description

Molybdenum precursor compound, method for preparing the same, and method for depositing a molybdenum-containing thin film using the same

The present invention relates to a molybdenum precursor compound, a preparation method thereof, a precursor composition for forming a molybdenum thin film including the same, a molybdenum-containing thin film using the same, and a deposition method thereof.

Molybdenum-containing metal films, molybdenum-containing oxide thin films, nitride thin films, sulfide thin films, and carbide thin films can be used as diffusion barriers, gate metals, and electrodes for metal wiring in semiconductor processes, and are used for industrial purposes. is widely used as a hard coating material, sensor, channel layer, and catalyst.

In particular, the molybdenum-containing nitride thin film has a large work function, so it is an important metal material that can suppress the leakage current of capacitors that require high permittivity due to integration in DRAM. In 3D NAND flash memory, it can replace tungsten (W) metal, which is currently used due to its low resistance, or can be used as a diffusion barrier for tungsten (W) metal, and furthermore, for growing molybdenum. It can be used as a diffusion barrier in a metal process in a non-memory field such as a seed layer and a logic device.

On the other hand, development of products such as high aspect ratio and complex shapes of three-dimensional structures in the memory field and non-memory field is diversifying, and molybdenum-containing metal films suitable for this, molybdenum-containing oxide A thin film or nitride film is required.

Molybdenum precursor compounds currently used as the molybdenum-containing thin film are known, such as MoCl ₅ and MoO ₂ Cl ₂ , but since these precursors are solid precursors, it is difficult to supply sources and may cause difficulties in the process. There may be a problem of poor mass productivity.

In addition, as molybdenum precursor compounds, Mo( ^tBuN ) ₂ (NMe ₂ ) ₂ and Mo(NMeEt) ₄ are known, but these precursor compounds are precursors in liquid form, but have poor thermal stability and have excellent film quality. There is a limit to forming a ribdenium-containing thin film.

As a result, it has excellent thermal stability and can exhibit excellent characteristics even at high temperatures, and is suitable for process temperatures for various application fields such as memory and non-memory fields. It is necessary to develop a molybdenum precursor compound capable of forming a thin film or nitride film, and furthermore, a novel molybdenum precursor compound that can be used for atomic layer deposition (ALD) that can overcome a high step ratio. It is in need of development.

Korean Patent Publication No. 2019-0024823

The present invention was devised to solve the problems of the prior art,

An object of the present invention is to exist in a liquid state at room temperature, which is advantageous to the manufacturing process, and can be deposited in a wide range of temperatures from low to high temperatures, has excellent thermal stability, and is effective in atomic layer deposition (ALD). It is to provide a novel molybdenum precursor compound capable of forming a molybdenum-containing metal film, a molybdenum-containing oxide thin film or a molybdenum-containing nitride thin film having a uniform thickness and excellent quality.

Another object of the present invention is to provide a method for preparing the molybdenum precursor compound in a safe and efficient manner.

Another object of the present invention is to provide a precursor composition for thin film deposition containing the molybdenum precursor compound.

Another object of the present invention is to provide a molybdenum-containing thin film having a uniform thickness and excellent quality even on various substrates by using the molybdenum precursor compound.

Another object of the present invention is to provide a method for depositing a molybdenum-containing thin film, wherein the molybdenum-containing thin film is deposited using the molybdenum precursor compound.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

The present invention provides a molybdenum precursor compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring;

X ₁ and X ₂ are each independently selected from oxygen (O), nitrogen (N), and carbon (C).

In addition, the present invention includes a step of reacting a compound represented by the following formula A with a compound represented by the formula B and a compound represented by the formula C in a solvent, and a molybdenum precursor represented by the formula 1 A method for preparing the compound is provided:

[Formula A]

In Formula A,

X _A and X _B are each independently a halogen element,

[Formula B]

[Formula C]

In Formulas B and C,

M ₁ and M ₂ are each independently an alkali metal or an alkaline earth metal;

Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring;

X ₁ and X ₂ are each independently selected from oxygen (O), nitrogen (N), and carbon (C).

In addition, the present invention provides a composition for forming a molybdenum thin film comprising the molybdenum precursor compound.

In addition, the present invention provides a composition for forming a molybdenum thin film deposited using a molybdenum precursor compound represented by the following formula (9):

[Formula 9]

In Formula 9,

R ₃ is selected from the group consisting of hydrogen, a linear or branched C ₁ -C ₆ alkyl group, and a substituted or unsubstituted C ₄ -C ₈ cyclic alkyl group.

In addition, the present invention provides a molybdenum-containing thin film formed using the molybdenum precursor compound.

In addition, the present invention provides a method for depositing a molybdenum-containing thin film, including depositing a molybdenum-containing thin film on a substrate using the molybdenum precursor compound.

The molybdenum precursor compound according to an embodiment of the present invention has excellent volatility, exists in a liquid state at room temperature, is advantageous to the manufacturing process, has low resistivity, excellent thermal stability, and has a wide range of temperatures from low to high temperatures Molybdenum-containing thin films can be easily formed by chemical vapor deposition (CVD) as well as atomic layer deposition (ALD).

In particular, when forming a molybdenum-containing thin film using the molybdenum precursor compound, it is easy to control the deposition rate, such as adjusting the deposition rate low or high, so that the desired thickness and composition of the thin film can be controlled, and the surface It is possible to form a thin film with excellent coverage and uniform thickness even on substrates with irregularities or patterns (grooves), porous substrates, plastic substrates, or substrates with complex three-dimensional structures, so high-quality molybdenum-containing thin films can be realized.

Therefore, the molybdenum precursor compound having the above properties is very effective with excellent properties depending on its use in various fields such as memory devices and logic devices, large-area display devices, and moisture penetration prevention films of organic light emitting diode (OLED) devices. In particular, it can be effectively used in a semiconductor process because of its high step ratio and easy fine thickness control.

1 is a ¹ H-NMR spectrum of molybdenum precursor compounds prepared according to Examples 1 to 6 of the present application.
Figure 2 is a graph of the results of thermogravimetric analysis (TGA) measurement of molybdenum precursor compounds prepared according to Examples 2, 5, and 6, and Comparative Examples 1 and 2 of the present application.
3 is a graph showing resistivity values of molybdenum-containing nitride thin films formed using molybdenum precursor compounds prepared according to Examples 2 and 6 of the present application.
4 is a transmission electron microscope (TEM) photograph of a molybdenum-containing nitride thin film formed using a molybdenum precursor compound prepared according to Example 2 of the present application.
5 is a TEM image of a molybdenum-containing nitride thin film formed using a molybdenum precursor compound prepared according to Example 6 of the present application.
6 is a TEM image of a molybdenum precursor compound prepared according to Example 6 of the present application at 350° C. and a molybdenum-containing nitride thin film formed using plasma.
7 is a TEM image of a molybdenum precursor compound prepared according to Example 6 of the present application at 400° C. and a molybdenum-containing nitride thin film formed using plasma.
8 is a TEM image of a molybdenum precursor compound prepared according to Example 6 of the present application at 450° C. and a molybdenum-containing nitride thin film formed using plasma.
9 is a component analysis of a molybdenum precursor compound prepared according to Example 6 of the present application at 350 ° C. and a molybdenum-containing nitride thin film formed using plasma using Auger electron spectroscopy (AES) This is the resulting graph.
10 is a graph of component analysis results of a molybdenum precursor compound prepared according to Example 6 of the present application at 400° C. using AES and a molybdenum-containing nitride thin film formed using plasma.
11 is a graph of component analysis results of a molybdenum precursor compound prepared according to Example 6 of the present application at 450° C. using AES and a molybdenum-containing nitride thin film formed using plasma.
12 is a graph showing film growth per ALD gas supply cycle (GPC) and resistivity values of a molybdenum precursor compound prepared according to Example 6 of the present application and a molybdenum-containing nitride thin film formed using plasma .

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

Advantages and features of the present invention, and methods of achieving them, will become clear with reference to the following examples. However, the present invention is not limited to the embodiments disclosed below and will be implemented in various forms different from each other, only these embodiments make the disclosure of the present invention complete, and common knowledge in the art to which the present invention pertains. It is provided to completely inform the person who has the scope of the invention, and the present invention is only defined by the scope of the claims.

In addition, in this specification, when a member is said to be “on” another member, this includes not only the case of being “directly on” another member, but also the case of having another member in the middle.

In this specification, when a certain component is said to "include", this means that it may further include other components, not excluding other components, unless otherwise stated.

It should be understood that all numbers and expressions representing amounts of constituents, reaction conditions, etc. described herein are modified by the term "about" in all cases unless otherwise specified.

In this specification, each of the terms "film" or "thin film" means both "film" and "thin film" unless otherwise specified.

As used herein, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups and all possible isomers thereof. For example, the alkyl or alkyl group is a methyl group (Me), an ethyl group (Et), a normal propyl group ( ⁿ Pr), an isopropyl group ( ⁱ Pr), a normal butyl group ( ⁿ Bu), an isobutyl group ( ⁱ Bu) , tert-butyl group (tert-Bu, ^t Bu), sec-butyl group ( ^sec Bu), etc., as well as isomers thereof, etc., but may not be limited thereto.

[Molybdenum precursor compound]

According to one embodiment of the present invention, a molybdenum precursor compound represented by Formula 1 is provided:

[Formula 1]

In Formula 1,

Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring;

X ₁ and X ₂ are each independently selected from oxygen (O), nitrogen (N), and carbon (C).

The molybdenum precursor compound has a higher volatility by including a carbocyclic ring or a heterocyclic ring bonded to the specific structure of Formula 1, particularly molybdenum (Mo), and is present in a liquid state at room temperature. It can be deposited in a wide range of temperatures from low to high temperatures and has excellent thermal stability, making it easy to form molybdenum-containing thin films by not only Chemical Vapor Deposition (CVD) but also Atomic Layer Deposition (ALD). can be formed

In particular, when a molybdenum-containing thin film is formed using the molybdenum precursor compound, a low resistivity (μΩ cm) value of, for example, 600 μΩ cm or less can be provided, requiring low resistivity and It can be used in various ways, such as gate electrodes, diffusion barriers, and capacitor electrodes used in DRAM, NAND flash, and logic devices. In addition, it is easy to control the deposition rate, such as by adjusting the deposition rate of the thin film low or high, so that the desired thickness and composition of the thin film can be controlled, and a substrate having irregularities or patterns (grooves) on the surface, a porous substrate, a plastic substrate, or Since a thin film having excellent coverage and uniform thickness can be formed even on a substrate having a complex three-dimensional structure, a high-quality molybdenum-containing thin film can be provided, and the molybdenum precursor compound is widely used in the electronic device field. It has technical significance in that it can be used very effectively for various purposes and can exhibit excellent characteristics.

Specifically, the molybdenum precursor compound may be represented by Formula 1 above. In the molybdenum precursor compound represented by Formula 1, the imido group attached to molybdenum (Mo) forms a double bond with the molybdenum (Mo) metal, thereby further enhancing the stability of the molybdenum precursor compound. By including a carbocyclic ring or a heterocyclic ring bonded to the molybdenum (Mo), the reaction is excellent and the reaction easily occurs on the surface, and the formation of a thin film is easy, and the thermal stability is very excellent, such as A low specific resistance of 600 μΩ cm or less can be realized, and the film density can be improved.

In the present specification, the carbocyclic ring refers to a monocyclic or polycyclic group having 3 to 20 carbon atoms (C ₃ -C ₂₀ ) including only carbon as a ring-forming atom. The C ₃ -C ₂₀ carbocyclic ring may include an aromatic carbocyclic group or a non-aromatic carbocyclic group, and may specifically include a non-aromatic carbocyclic group.

In addition, in the present specification, the heterocyclic ring has the same structure as the C ₃ -C ₂₀ carbocyclic ring, but as a ring-forming atom, in addition to carbon (which may have 1 to 20 carbon atoms), oxygen ( O), nitrogen (N), and carbon (C) refers to a group containing at least one heteroatom selected from. Specifically, the heterocyclic ring includes at least one hetero atom selected from oxygen (O), nitrogen (N), and carbon (C), such as at least two, such as 1 to 4, or such as 1 to 4 heteroatoms. Can contain 3.

In addition, the substituents in the substituted C ₃ -C ₂₀ carbocyclic ring and the substituted C ₁ -C ₂₀ heterocyclic ring are each independently a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, A C ₂ -C ₂₀ alkynyl group and a C ₁ -C ₂₀ alkoxy group may be included. For example, the substituents may each independently include a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₁₅ alkyl group, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₀ alkyl group, or a C ₁ -C ₈ alkyl group.

In Formula 1, for example, Cy ₁ and Cy ₂ may each independently be selected from a substituted or unsubstituted C ₃ -C ₁₅ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₁₅ heterocyclic ring. there is. For example, Cy ₁ and Cy ₂ may each independently be selected from a substituted or unsubstituted C ₃ -C ₁₂ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₁₂ heterocyclic ring. For example, Cy ₁ and Cy ₂ may each independently be selected from a substituted or unsubstituted C ₃ -C ₁₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₁₀ heterocyclic ring. For example, Cy ₁ and Cy ₂ may each independently be selected from a substituted or unsubstituted C ₃ -C ₈ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₈ heterocyclic ring. For example, Cy ₁ and Cy ₂ may each independently be selected from a substituted or unsubstituted C ₅ -C ₈ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₈ heterocyclic ring.

According to an embodiment of the present invention, the molybdenum precursor compound may be represented by Formula 2 below:

[Formula 2]

In Formula 2,

Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring, specifically Cy ₁ and Cy ₂ is each independently selected from a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring.

In particular, as shown in Chemical Formula 2, the cyclic amine bonded to molybdenum (Mo) has excellent reactivity, so that the reaction easily occurs on the surface, so it is easy to form a thin film, and a stable molybdenum-containing metal film, oxide thin film or It is easy to form a nitride thin film and has good adhesion to a substrate, so that a molybdenum-containing metal film is formed through reaction with hydrogen (H ₂ ), an oxide film through reaction with ozone (O ₃ ), which has a high oxidizing power, It is advantageous to form a nitrided thin film by reacting with ammonia (NH ₃ ) having high nitriding power. In addition, it has high stability and can be deposited at a high temperature of 300° C. to 550° C., for example, 350° C. to 550° C., and the film density can be improved.

According to another embodiment of the present invention, the molybdenum precursor compound may be represented by Formula 3 below:

[Formula 3]

In Formula 3,

Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₁ -C ₁₀ heterocyclic ring, and Y ₁ and Y ₂ are each independently oxygen (O), nitrogen (N), and carbon. (C) is selected from.

Specifically, in Chemical Formula 3, Cy ₁ and Cy ₂ may each independently be a substituted or unsubstituted C ₁ -C ₆ heterocyclic group. Or, in Formula 3, Cy ₁ and Cy ₂ are each independently a substituted or unsubstituted C ₂ -C ₆ heterocyclic ring, a substituted or unsubstituted C ₃ -C ₆ heterocyclic ring, and a substituted or unsubstituted C 3 -C 6 heterocyclic ring. It may be selected from C ₄ -C ₆ heterocyclic rings.

Also, in Chemical Formula 3, Y ₁ and Y ₂ may each independently be selected from oxygen (O), nitrogen (N), and carbon (C). For example, in Chemical Formula 3, Y ₁ and Y ₂ may each independently represent oxygen (O). For example, in Chemical Formula 3, Y ₁ and Y ₂ may each independently represent nitrogen (N). For example, in Chemical Formula 3, Y ₁ and Y ₂ may each independently represent carbon (C).

According to one embodiment of the present invention, in Formula 3, Cy ₁ and Cy ₂ are each independently substituted or unsubstituted pyrrolidine, piperidine, morpholine, and It may be selected from piperazine. For example, Cy ₁ and Cy ₂ are each independently pyrrolidine, piperidine, morpholine, 1-methylpiperazine and 2-methylpiperidine ( 2-methylpiperidine).

A molybdenum precursor compound according to another embodiment of the present invention may be a compound represented by one of Formulas 4 to 8:

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

, 및

, and

[Formula 8]

.

.

The molybdenum precursor compound according to an embodiment of the present invention has excellent thermal stability, can be applied from 300 ° C to 550 ° C, and exists in a liquid state at room temperature, so that molybdenum- It is possible to form a containing thin film. In particular, the molybdenum precursor compound easily deposits a molybdenum-containing metal film, a molybdenum-containing oxide film, and a molybdenum-containing nitride film having uniform and excellent film properties in atomic layer units by ALD. There are great advantages to being able to do it.

When forming a molybdenum-containing thin film by ALD using the molybdenum precursor compound, 0.5 Å / cycle or more, 0.7 Å / cycle or more in a temperature range of 300 ° C to 550 ° C, for example, 300 ° C to 500 ° C , 0.8 Å / cycle or more, 1.0 Å / cycle or more, 2.0 Å / cycle or less, 1.8 Å / cycle or less, 1.5 Å / cycle or less, 1.2 Å / cycle or less, for example, an ALD gas supply cycle of 0.5 to 1.5 Å / cycle Sugar film growth (GPC) can be achieved.

When the GPC in the above range is satisfied, it may be more advantageous to control the desired doping amount of molybdenum when forming a molybdenum-containing thin film. In particular, the molybdenum precursor compound according to an embodiment of the present invention Compared to general molybdenum precursor compounds, GPC can be controlled to be low, so it can achieve the desired step ratio and thickness in processes such as DRAM capacitors requiring high step ratio and fine thickness control, as well as especially very thin Since it is possible to provide a high-quality molybdenum-containing thin film having a thickness and excellent physical properties and covering properties, the molybdenum precursor compound has a great advantage in that it can be used very effectively for various purposes in the field of semiconductor devices. there is.

In addition, the molybdenum precursor compound may have a density of 1.0 g/mol to 1.5 g/mol at 25°C. When the molybdenum precursor compound satisfies the above density range, since it is in a liquid state, there may be an advantage when supplying a source. This advantage is very significant in terms of process or performance compared to molybdenum precursor compounds, such as MoO ₂ Cl ₂ , which are difficult to source as a precursor in solid form and have difficulties in process and poor mass productivity, for example, MoO 2 Cl 2 can be advantageous

In addition, the molybdenum precursor compound may have a vapor pressure of 0.1 to 1.5 torr at a temperature of about 100 °C. When the vapor pressure range is satisfied, there is an advantage in that the source can be supplied using a bypass or bubbling method, which can be advantageous in terms of process.

In addition, the molybdenum precursor compound may have a boiling point (bp) of, for example, 80 °C to 120 °C, for example, 90 °C to 115 °C, or 100 °C to 110 °C.

According to one embodiment of the present invention, the molybdenum precursor compound is heated from room temperature to 500 ° C. at a heating rate of 10 ° C. / min using thermogravimetric analysis (TGA), and the weight of the molybdenum precursor compound TG ₅₀ (°C), the temperature at which the reduction is 50%, such as 180°C to 300°C, such as 180°C to 250°C, such as 185°C to 300°C, such as 188°C to 280°C, such as 188°C to 250°C, or For example, it may be 200 °C to 250 °C. The TG ₅₀ (°C) may be, for example, 180°C to 250°C.

According to one embodiment of the present invention, the molybdenum precursor compound has a residual weight (W ₅₀₀ ) of the molybdenum precursor compound at 500 ° C. when measured by thermogravimetric analysis (TGA), for example less than 20% by weight, for example 15 wt% or less, such as less than 15 wt%, such as 13 wt% or less, such as 12 wt% or less, such as 10 wt% or less, such as 8 wt% or less, such as 7 wt% or less, such as 5 wt% or less, such as 4.5 wt% % or less, such as 3 wt% or less, such as 2 wt% or less, such as 1.5 wt% or less, such as 1 wt% or less, or such as 0.5 wt% or less.

Specifically, the molybdenum precursor compound may have a residual weight (W ₅₀₀ ) of 1.5 wt % or less at 500° C. when measured by thermogravimetric analysis (TGA).

According to one embodiment of the present invention, the molybdenum precursor compound may have a weight retention rate (WR ₅₀₀ ) of 80% or more of Equation 1 below.

In Equation 1 above,

W ₂₅ is the initial weight of the molybdenum precursor compound at 25° C.;

W ₅₀₀ is the weight of the molybdenum precursor compound at 500°C when the temperature is raised from 25°C to 500°C at a heating rate of 10°C/min.

Specifically, the molybdenum precursor compound has a weight residual ratio (WR ₅₀₀ ) of, for example, 85% by weight or more, such as 87% by weight or more, such as 88% by weight or more, such as 89% by weight or more, such as 90% by weight or more, such as 92 wt% or more, such as 93 wt% or more, such as 95 wt% or more, such as 97 wt% or more, or such as 98 wt% or more. The molybdenum precursor compound has excellent volatility when the weight retention ratio (WR ₅₀₀ ) satisfies the above range, for example, at a temperature range of 300 ° C or higher, specifically 300 ° C to 550 ° C, for example 350 ° C to 550 ° C It can be more advantageous to form a molybdenum-containing metal film, an oxide thin film, and a nitride thin film, and in particular, there is a great advantage that uniform and excellent film properties can be implemented in atomic layer units by ALD.

[Method for Producing Molybdenum Precursor Compound]

According to one embodiment of the present invention, a method for producing a molybdenum precursor compound represented by Chemical Formula 1 is provided.

The molybdenum precursor compound represented by Formula 1 may be prepared by various methods.

The method for preparing the molybdenum precursor compound according to an embodiment of the present invention includes reacting a compound represented by Formula A below with a compound represented by Formula B and a compound represented by Formula C below in a solvent. can do:

[Formula A]

In Formula A,

X _A and X _B are each independently a halogen element,

[Formula B]

[Formula C]

In Formulas B and C,

M ₁ and M ₂ are each independently an alkali metal or an alkaline earth metal;

Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring;

X ₁ and X ₂ are each independently selected from oxygen (O), nitrogen (N), and carbon (C).

In Formula A, X _A and X _B are each independently F, Cl, Br, or I, and in Formulas B and C, M _One and M ₂ are each independently Li, Na, K, or Mg. can

Specifically, the molybdenum precursor compound represented by Formula 1 may be prepared by reacting as shown in Scheme 1 below.

[Scheme 1]

Step 1:

Step 2:

In Scheme 1 above,

X _A , X _B , M ₁ , M ₂ , Cy ₁ , Cy ₂ , X ₁ and X ₂ are as defined above.

As shown in Reaction Scheme 1, the molybdenum precursor compound of Formula 1 is optionally formed with a halide of Formula A in a solvent, such as a polar solvent, a non-polar solvent, or a mixture thereof, and a cyclic compound of Formula B and 　C. It can be easily obtained by performing a substitution reaction of a ring (ring) such as a cyclic amine (ie, a halide-cyclic amine substitution reaction) and then purifying it.

The molar ratio between the compound represented by Formula A and the compound represented by Chemical Formulas 　Ｂ　 and 　Formula 　C may be 1 to 2.5, for example 1 to 2.

The halide-cyclic amine substitution reaction may be performed in a solvent at 25°C to 50°C for 12 to 24 hours.

As the solvent, dimethoxyethane containing oxygen in the first step of Reaction Scheme 1 for the synthesis of the coordination, and in the second step of Reaction Scheme 1, an alkane having 5 to 8 carbon atoms, toluene, ether, tetrahydrofuran, and mono to tetra At least one selected from the group consisting of ethylene glycol dimethyl ether may be used, for example, hexane, pentane, toluene, or a combination thereof may be used, and specifically, hexane is selected because it has a stable boiling point of 78 ° C. it is desirable

According to one embodiment of the present invention, for example, a method for preparing a molybdenum precursor compound represented by Chemical Formula 5 from the molybdenum precursor compound is as follows.

In the compound represented by Chemical Formula 5, each of Cy ₁ and Cy ₂ is a piperidine group, and as shown in Scheme 1, a bis-thusher is formed in a mixture of toluene, a weakly polar solvent, and hexane, a non-polar solvent. Byutylimido-dichloro-molybdenum-dimethoxyethane coordination ( ^t BuN) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ ) and lithium piperidine (Li-N(CH ₂ ) ₅ ) were slowly added dropwise. After the reaction solution can be stirred at room temperature for 12 hours.

After the reaction is completed, the solvent is removed under reduced pressure and distilled under reduced pressure to obtain a molybdenum precursor compound represented by Formula 5 below. In order to suppress the decomposition reaction due to moisture or oxygen during the reaction, the reaction may be performed under a nitrogen (N ₂ ) or argon (Ar) stream.

[Precursor composition for thin film deposition]

According to one embodiment of the present invention, a composition for forming a molybdenum thin film including the molybdenum precursor compound represented by Formula 1 is provided.

In addition, a composition for forming a molybdenum thin film deposited using a molybdenum precursor compound represented by Formula 9 is provided:

[Formula 9]

In Formula 9,

R ₃ is selected from the group consisting of hydrogen, a linear or branched C ₁ -C ₆ alkyl group, and a substituted or unsubstituted C ₄ -C ₈ cyclic alkyl group.

In addition, the molybdenum precursor compound may be, for example, a molybdenum precursor compound represented by Formula 10 below:

[Formula 10]

The composition is water vapor (H ₂ O), oxygen (O ₂ ), oxygen plasma (O ₂ Plasma), nitric oxide (NO, N ₂ O), nitric oxide plasma (N ₂ O Plasma), oxygen nitride (N ₂ O ₂ ), hydrogen peroxide (H ₂ O ₂ ), and ozone (O ₃ ) an oxygen source including one or more selected from the group consisting of; and nitrogen (N ₂ ), ammonia (NH ₃ ), ammonia plasma (NH ₃ Plasma), hydrazine (N ₂ H ₄ ), and a nitrogen source including at least one selected from the group consisting of nitrogen plasma (N ₂ Plasma). can include more. In addition, the composition may further include hydrogen (H ₂ ).

Specifically, the composition may include, for example, at least one selected from the group consisting of hydrogen (H ₂ ), nitrogen (N ₂ ), and ammonia (NH ₃ ).

The composition may be, for example, water vapor (H ₂ O), oxygen (O ₂ ), oxygen plasma (O ₂ Plasma), nitrogen oxide (NO, N ₂ O), nitric oxide plasma (N ₂ O Plasma), oxygen nitride (N ₂ O ₂ ), hydrogen peroxide (H ₂ O ₂ ), and ozone (O ₃ ) may include one or more selected from the group consisting of.

The composition may include, for example, at least one selected from the group consisting of ammonia (NH ₃ ), ammonia plasma (NH ₃ Plasma), hydrazine (N ₂ H ₄ ), and nitrogen plasma (N ₂ Plasma).

More specifically, the composition may include at least one selected from the group consisting of hydrogen (H ₂ ), ozone (O ₃ ) and ammonia (NH ₃ ).

[Molybdenum-containing thin film]

According to one embodiment of the present invention, a molybdenum-containing thin film formed using the molybdenum precursor compound represented by Chemical Formula 1 can be provided.

According to one embodiment of the present invention, a molybdenum-containing thin film formed using the molybdenum precursor compound represented by Chemical Formula 9 or the composition for forming a molybdenum thin film may be provided.

The molybdenum-containing thin film may have a thickness of several nanometers (nm) to several micrometers (μm), and may be applied in various ways depending on the application purpose.

For example, the molybdenum-containing thin film has a thickness of about 1 nm or more, about 5 nm or more, about 10 nm or more, about 15 nm or more, about 20 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or greater, about 40 nm or greater, about 45 nm or greater, or about 50 nm or greater. In addition, the molybdenum-containing thin film has a thickness of about 500 nm or less, about 450 nm or less, about 400 nm or less, about 350 nm or less, about 300 nm or less, about 250 nm or less, about 200 nm or less, about 150 nm or less, or about 100 nm or less. Specifically, the thickness of the molybdenum-containing thin film may be variously selected from about 1 nm to about 500 nm.

The molybdenum-containing thin film may be formed on a substrate (substrate).

The substrate may use a molybdenum semiconductor wafer, a compound semiconductor wafer, or plastic substrates (PI, PET, PES), but may not be limited thereto. A substrate having holes or grooves may be used, and a porous substrate having a large surface area may be used.

The molybdenum precursor compound according to one embodiment of the present invention has a specific structure of Formula 1 or Formula 9, and thus has a low density and high thermal stability, so that it can be used as a molybdenum-containing thin film in various temperature ranges by CVD and ALD. can be efficiently formed, in particular, on substrates having patterns (grooves) or fine irregularities on the surface, porous substrates, and plastic substrates in the temperature range of 300 ° C to 550 ° C. A denium-containing thin film, such as a molybdenum-containing metal film, a molybdenum-containing oxide thin film, or a molybdenum-containing nitride thin film, can be uniformly formed, and the deepest part of fine irregularities or patterns (grooves) can be formed. It has an excellent effect of uniformly forming the molybdenum-containing thin film on the entire surface of the substrate, including the surface and the upper surface of the fine irregularities or patterns (grooves).

According to one embodiment of the present invention, the molybdenum-containing thin film has an aspect ratio of 1 to 50 and a width of 10 nm to 1 μm, or less. there is.

Specifically, the aspect ratio may be about 1 or more, about 2 or more, about 3 or more, about 5 or more, about 7 or more, about 10 or more, or about 15 or more. Alternatively, the aspect ratio may be about 50 or less, about 45 or less, about 40 or less, about 35 or less, about 30 or less, about 25 or less, or about 20 or less.

In addition, the width may be about 10 nm or more, about 15 nm or more, about 20 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, or about 40 nm or more. Alternatively, the width may be about 1 μm or less, about 900 nm or less, about 800 nm or less, about 700 nm or less, about 600 nm or less, about 500 nm or less, or about 450 nm or less.

The molybdenum-containing thin film may be at least one selected from the group consisting of a molybdenum-containing metal film, a molybdenum-containing oxide thin film, and a molybdenum-containing nitride thin film.

In addition, the molybdenum-containing thin film according to an embodiment of the present invention may have a low resistivity (μΩ cm) of 600 μΩ cm or less.

Specifically, the resistivity of the molybdenum-containing thin film is, for example, 400 to 600 μΩ cm, for example 450 to 600 μΩ cm, for example 500 to 600 μΩ cm, for example 450 to 590 μΩ cm, for example 500 to 588 μΩ cm, such as 500 to 580 μΩ cm, such as 500 to 570 μΩ cm, such as 500 to 560 μΩ cm, such as 500 to 550 μΩ cm, such as 500 to 530 μΩ cm, or such as 500 to 520 μΩ cm can be cm. In addition, the resistivity of the molybdenum-containing thin film may be, for example, 550 to 590 μΩ cm, 560 to 590 μΩ cm, or 560 to 588 μΩ cm, for example.

Specifically, the resistivity of the molybdenum-containing thin film may be 400 to 600 μΩ·cm in the case of a molybdenum nitride film and 20 to 50 μΩ·cm in the case of a molybdenum metal film.

Therefore, the molybdenum-containing thin film can be used for gate electrodes, diffusion barriers, and capacitor electrodes used in DRAM or NAND flash, logic devices, etc. requiring low resistivity, and can be applied in various ways depending on the application. It can be.

[Deposition method of molybdenum-containing thin film]

According to one embodiment of the present invention, a molybdenum-containing thin film comprising the step of depositing a molybdenum-containing thin film on a substrate (substrate) using the molybdenum precursor compound represented by Formula 1 A deposition method is provided.

According to another embodiment of the present invention, depositing a molybdenum-containing thin film on a substrate (substrate) using the molybdenum precursor compound represented by Formula 9 or the composition for forming a molybdenum thin film To provide a method for depositing a molybdenum-containing thin film.

Specifically, a molybdenum-containing metal film, a molybdenum-containing oxide thin film, or a molybdenum-containing nitride is supplied to a substrate by supplying the molybdenum precursor compound represented by Chemical Formula 1 or the film deposition composition in a gaseous state. Forming a thin film may include, but is not limited thereto.

The description is as described above.

The method of depositing the thin film may use a method and/or apparatus known in the art of the present application, and if necessary, may be performed by using one or more additional reaction gases together.

According to one embodiment of the present invention, in the method of depositing the molybdenum-containing thin film, after accommodating the substrate in the reaction chamber, the molybdenum precursor compound is deposited on the substrate using a carrier gas or a diluent gas. Transfer to deposit the molybdenum-containing thin film.

Specifically. The deposition is carried out at a temperature of 300 ° C to 550 ° C, for example, 350 ° C to 550 ° C by chemical vapor deposition (CVD), specifically organometallic chemical vapor deposition (MOCVD), or atomic layer deposition (ALD). ) can be performed by

In particular, a molybdenum-containing metal film, a molybdenum-containing oxide thin film, or a molybdenum-containing nitride at a temperature range of 300° C. to 550° C. even on a substrate having a pattern (groove) or a porous substrate or a plastic substrate. The thin film can be uniformly formed, the aspect ratio is about 1 to 50, or more, and the width is about 1 μm to 10 nm, or the deepest surface of the fine pattern (groove) and the fine pattern (groove) ) It is possible to form a uniform thin film on the substrate including the surface of.

Here, the deposition temperature of 300 ° C to 550 ° C, for example, 350 ° C to 550 ° C, can be applied to memory devices, logic devices, and display devices, and since the process temperature is wide, the deposition temperature is applicable to various fields. It is preferable that deposition takes place in

In addition, it is preferable to use at least one mixed gas selected from the group consisting of argon (Ar), nitrogen (N ₂ ), helium (He), and hydrogen (H ₂ ) as the transport gas or diluent gas.

In addition, as a method of delivering the molybdenum precursor compound onto the substrate, a bubbling method in which the molybdenum precursor compound is forcibly vaporized using a transport gas or a diluent gas, and a vaporizer by supplying the molybdenum precursor compound in a liquid phase at room temperature A liquid supply system that vaporizes through (liquid delivery system, LDS) method; At least one method selected from the group consisting of a vapor flow control (VFC) method in which vapor pressure of a precursor is directly supplied and a bypass method may be used.

For example, when the vapor pressure is high, a vapor flow control (VFC) method may be used, and when the vapor pressure is low, a bypass for vaporizing by heating the container; And at least one supply method selected from the group consisting of a bubbling method using argon (Ar) or nitrogen (N ₂ ) gas may be applied.

More specifically, the delivery method includes a bubbling method or a bypass method of vaporizing by heating, and the bubbling method includes 0.1 to 10 torr and 100 ° C to 150 ° C. It is performed using a transport gas at a temperature range of, and the bypass method of vaporizing by heating may be performed using a vapor pressure of 0.1 to 1.5 torr at a temperature range of room temperature to 100 ° C.

In addition, in order to vaporize the molybdenum precursor compound, for example, argon (Ar) or nitrogen (N ₂ ) gas may be transported, thermal energy or plasma may be used during deposition, or a bias may be applied on the substrate.

Meanwhile, in order to deposit a molybdenum-containing metal film when depositing the thin film, at least one selected from the group consisting of hydrogen (H ₂ ), neutral nitrogen (N ₂ ), and ammonia (NH ₃ ) may be used as a reaction gas. can

In addition, when depositing the thin film, in order to deposit a molybdenum-containing oxide thin film (Mo ₂ O _3, MoO ₃ ), water vapor (H ₂ O), oxygen (O ₂ ), and oxygen plasma (O ₂ Plasma ), nitric oxide (NO, N ₂ O), nitric oxide plasma (N ₂ O Plasma), oxygen nitride (N ₂ O ₂ ), hydrogen peroxide (H ₂ O ₂ ), and from the group consisting of ozone (O ₃ ) One or more selected species may be used.

In addition, in order to deposit a molybdenum-containing nitride thin film (MoN, MN) when depositing the thin film, ammonia (NH ₃ ), ammonia plasma (NH ₃ Plasma), hydrazine (N ₂ H ₄ ), and nitrogen as reaction gases At least one selected from the group consisting of plasma (N ₂ Plasma) may be used.

The present invention will be described in more detail by the following examples. The following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto.

Example

<Preparation Example 1> Bis-tertiary butylimido-dichloro-molybdenum-dimethoxyethane

Preparation of coordination: ( ^t BuN) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ )

In a flame-dried 3L Schlenk flask, about 70 g (about 0.34 mol) of sodium molybdate (Na ₂ MoO ₄ ) and about 2000 ml of dimethoxyethane (C ₄ H ₁₀ O ₂ ) were put and maintained at room temperature. While stirring the mixture in the flask, about 137.59 g (about 1.36 mol) of triethylamine ((C ₂ H ₅ ) ₃ N) and about 295.4 g (about 2.72 mol) of trimethylchlorosilane ((CH ₃ ) ₃ SiCl) were sequentially added. was added dropwise slowly. At this time, fumes were generated and a white solid was produced. About 49.7 g (about 0.68 mol) of tertiary butylamine ( ^tBuNH ₂ ) was slowly added dropwise to the flask, and then the reaction solution was stirred for about 12 hours while refluxing. After the reaction was completed, salts generated during the reaction were removed through filtration, and solvents and volatile side reactants were removed under reduced pressure to obtain 125 g of a dark green solid.

¹ H-NMR (400 MHz, CDCl ₃ , 25° C.): δ 3.85, (m, 4H, CH ₃ OCH ₂ CH ₂ OCH ₃ ), δ 3.78 (s, 6H, CH ₃ OCH ₂ CH ₂ OCH ₃ ), δ 1.53 (s, 18H, (CH ₃ ) ₃ CN)Mo)

<Example 1> Preparation of bis-tertiarybutylimido-dipyrrolidinyl-molybdenum: ( ^t BuN) ₂ Mo[N(CH ₂ ) ₄ ] ₂

[Formula 4]

Put about 13.9 g (about 0.2 mol) of pyrrolidine (C ₄ H ₉ N) and about 500 ml of toluene (C _-7 H ₈ ) into a flame-dried 1L Schlenk flask, and set the temperature to -10 to 0 ° C. kept After slowly adding about 52.1 g (about 0.2 mol) of n-butyl lithium (n-BuLi, 23%) dropwise using a cannula, the temperature was raised to room temperature and stirred for 3 hours to form Li-N(CH ₂ ) ₄ got it

About 39 g of the bis-tertiarybutylimido-dichloro-molybdenum-dimethoxyethane ligand ( ^tBuN ) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ ) obtained in Preparation Example 1 was placed in another flame-dried 2L Schlenk flask. (0.1 mol) and toluene (toluene, C _-7 H ₈ ) into about 500ml was maintained at -30 ℃ to -20 ℃. Here, pre-synthesized Li-N(CH ₂ ) ₄ was slowly added dropwise, and the temperature was slowly raised to 50° C., followed by stirring for 12 hours. After the reaction was completed, salts generated during the reaction were removed through filtration, and about 25 g of a brown liquid of Chemical Formula 4 (yield: about 66%) was obtained by distilling the solvent and volatile side reactants under reduced pressure.

Density: 1.32 g/mol (at 25°C)

Boiling point (bp): 101℃ (0.3 torr) (309.4℃ at 760mmHg)

¹ H-NMR (400 MHz, C ₆ D ₆ , 25° C.): δ 4.035, 4.023, 4.011 (t, 8H, MoN(CH ₂ CH ₂ CH ₂ CH ₂ )), δ 1.569, 1.554 (m, 8H, MoN(CH ₂ CH ₂ CH ₂ CH ₂ )), δ 1.444 (s, 18H, (CH ₃ ) ₃ CNMo)

<Example 2> Preparation of bis-tertiarybutylimido-dipiperidinyl-molybdenum: ( ^t BuN) ₂ Mo[N(CH ₂ ) ₅ ] ₂

[Formula 5]

About 16.6 g (about 0.2 mol) of piperidine (C ₅ H ₁₁ N) and about 500 ml of toluene (C _-7 H ₈ ) were added to a flame-dried 1L Schlenk flask, and the temperature was set to -10 to 0 ° C. kept After slowly adding about 52.1 g (about 0.2 mol) of n-butyl lithium (n-BuLi, 23%) dropwise using a cannula, the temperature was raised to room temperature and stirred for 3 hours to obtain Li-N (CH ₂ ) got ₅ .

In another flame-dried 2L Schlenk flask, 39 g of the bis-tertiarybutylimido-dichloro-molybdenum-dimethoxyethane coordination ( ^tBuN ) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ ) obtained in Preparation Example 1 ( 0.1 mol) and toluene (toluene, C _-7 H ₈ ) into about 500ml was maintained at about -30 ℃ to -20 ℃. After slowly adding Li—N(CH ₂ ) ₅ synthesized in advance thereto, the temperature was slowly raised to about 50° C. and the mixture was stirred for about 12 hours. After the reaction was completed, the salt generated during the reaction was removed through filtration, and the solvent and volatile side reactants were distilled under reduced pressure to obtain about 27 g (yield of about 66.4%) of a yellow liquid of Chemical Formula 5.

Density: 1.33 g/mol (at 25°C)

Boiling point (bp) 103℃ (0.26 torr) (314.9℃ at 760mmHg)

¹ H-NMR (400 MHz, C ₆ D ₆ , 25° C.): δ 3.896, 3.883, 3.870 (t, 8H, MoN(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ )) δ 1.616, 1.604 (m, 8H , MoN(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ )), δ 1.491, 1.475 (m, 4H, MoN(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ )) δ 1.413 (s, 18H, (CH ₃ ) _3CNMo )

<Example 3> Preparation of bis-tertiarybutylimido-dimorpholino-molybdenum: ( ^tBuN ) ₂ Mo[N(CH ₂ ) ₂ O(CH ₂ ) ₂ )] ₂

[Formula 6]

Put about 18.73 g (about 0.2 mol) of morpholine (C ₄ H ₉ NO) and about 500 ml of toluene (C _-7 H ₈ ) into a flame-dried 1L Schlenk flask, and set the temperature to about -10 ℃ to 0 ℃ was maintained as After slowly adding about 52.1 g (about 0.2 mol) of n-butyl lithium (n-BuLi, 23%) dropwise using a cannula, the temperature was raised to room temperature and stirred for 3 hours to obtain Li-N (CH ₂ ) ₂ O(CH ₂ ) ₂ was obtained.

In another flame-dried 2L Schlenk flask, the bis-tertiarybutylimido-dichloro-molybdenum-dimethoxyethane ligand ( ^t BuN) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ ) obtained in Preparation Example 1 was about 39 g. (about 0.1 mol) and toluene (toluene, C _-7 H ₈ ) into about 500ml was maintained at about -30 ℃ to -20 ℃. After slowly adding Li—N(CH ₂ ) ₂ O(CH ₂ ) ₂ previously synthesized here, the temperature was slowly raised to 50° C., and stirred for 12 hours. After the reaction was completed, the salt generated during the reaction was removed through filtration, and the solvent and volatile side reactants were distilled under reduced pressure to obtain about 22 g (yield: about 53.6%) of a brown liquid of Chemical Formula 6.

Density: 1.31 g/mol (at 25°C)

Boiling point (bp) 108℃ (0.3 torr) (319.2℃ at 760mmHg)

¹ H-NMR (400 MHz, C ₆ D ₆ , 25° C.): δ 3.761, 3.749, 3.737 (t, 8H, MoN(CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ )) δ 3.667, 3.655, 3.643 (t , 8H, MoN(CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ )), δ 1.299 (s, 18H, (CH ₃ ) ₃ CNMo)

<Example 4> Preparation of bis-tertiarybutylimido-bis-4-methylpiperazinyl-molybdenum: ( ^tBuN ) ₂ Mo[N(CH ₂ ) ₂ N(CH ₃ )(CH ₂ ) ₂ ] ₂

[Formula 7]

Put about 72.12g (0.72mol) of 1-methylpiperazine (C ₅ H ₁₂ N ₂ ) and about 1000ml of toluene (C _-7 H ₈ ) into a flame-dried 2L Schlenk flask, and set the temperature to about -10℃. to 0 °C. After slowly adding about 192.2 g (about 0.72 mol) of n-butyl lithium (n-BuLi, 23%) dropwise using a cannula, the temperature was raised to room temperature and stirred for 3 hours to obtain Li-[N(CH ₂ ) ₂ N(CH ₃ )(CH ₂ ) ₂ ] was obtained.

About 125 g of the bis-tertiarybutylimido-dichloro-molybdenum-dimethoxyethane ligand ( ^tBuN ) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ ) obtained in Preparation Example 1 was placed in another flame-dried 3L Schlenk flask. (about 0.31 mol) and toluene (toluene, C _-7 H ₈ ) into about 1000ml was maintained at about -30 ℃ to -20 ℃. After slowly adding Li-[N(CH ₂ ) ₂ N(CH ₃ )(CH ₂ ) ₂ ] synthesized in advance thereto, the temperature was slowly raised to 50° C., and stirred for 12 hours. After the reaction was completed, the salt generated during the reaction was removed through filtration, and the solvent and volatile side reactants were distilled under reduced pressure to obtain about 70 g (yield: about 51.7%) of an orange liquid of Chemical Formula 7.

Density: 1.34 g/mol (at 25°C)

Boiling Point (bp) 121℃ (0.38 torr) (332.5℃ at 760mmHg)

¹ H-NMR (400 MHz, C ₆ D ₆ , 25° C.): δ 3.986, 3.974, 3.963 (t, 8H, MoN(CH ₂ CH ₂ N(CH ₃ )CH ₂ CH ₂ )) δ 2.397, 2.385, 2.373 (t, 8H, MoN(CH ₂ CH ₂ N(CH ₃ )CH ₂ CH ₂ )), δ 2.143 (s, 3H, MoN(CH ₂ CH ₂ N(CH ₃ )CH ₂ CH ₂ )) δ 1.382 (s, 18H, (CH ₃ ) ₃ CNMo)

<Example 5> Preparation of bis-tertiarybutylimido-bis-2-methylpiperidinyl-molybdenum: ( ^tBuN ) ₂ Mo[NCH(CH ₃ )(CH ₂ ) ₄ ] ₂

[Formula 8]

Put about 39.25g (0.35mol) of 2-methylpiperidine (C ₆ H ₁₃ N) and about 500ml of toluene (C _-7 H ₈ ) into a flame-dried 1L Schlenk flask and set the temperature to about -10 ° C. It was maintained at 0°C. After slowly adding about 106.3 g (about 0.35 mol) of n-butyl lithium (n-BuLi, 23%) dropwise using a cannula, the temperature was raised to room temperature and stirred for 3 hours to Li-[NCH(CH ₃ )(CH ₂ ) ₄ ] was obtained.

In another flame-dried 2L Schlenk flask, the bis-tertiarybutylimido-dichloro-molybdenum-dimethoxyethane ligand ( ^t BuN) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ ) obtained in Preparation Example 1 was about 69.8 g (about 0.175 mol) and toluene (toluene, C _-7 H ₈ ) into about 500ml was maintained at about -30 ℃ to -20 ℃. Pre-synthesized Li-[NCH(CH ₃ )(CH ₂ ) ₄ ] was slowly added thereto dropwise, and then the temperature was slowly raised to room temperature, followed by stirring for 12 hours. After the reaction was completed, salts generated during the reaction were removed through filtration, and 50 g of the brown liquid of Chemical Formula 8 (yield: 65.75%) was obtained by distilling the solvent and volatile side reactants under reduced pressure.

Density: 1.35 g/mol (at 25°C)

Boiling point (bp) 110℃ (0.3 torr) (322℃ at 760mmHg)

¹ H-NMR (400 MHz, C ₆ D ₆ , 25° C.): δ 4.251 (m, 2H, MoN(NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 3.776 (m, 2H, MoN (NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 3.631 (m, 1H, MoN(NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 3.509 (m, 1H, MoN (NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 1.700 (m, 4H, MoN(NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 1.575 (m, 4H, MoN (NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 1.489, 1.472 (d, 3H, MoN(NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 1.459, 1.441 (d , 3H, MoN(NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 1.338 (m, 4H, MoN(NCH(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ )) δ 1.433, 1.423 , 1.412 (t, 18H, (CH ₃ ) ₃ CNMo)

<Example 6> Preparation of bis-tertiarybutylimido-cyclopentadienyl-methyl-molybdenum: ( ^t BuN) ₂ MoCp(CH ₃ )

[Formula 10]

Put about 12.8 g (about 0.193 mol) of cyclopentadiene (C ₅ H ₅ ) and about 500 ml of n-hexane (C ₆ H ₁₄ ) into a flame-dried 1L Schlenk flask, and set the temperature to about -10 ℃ to Maintain at 0°C. After slowly adding about 51.5 g (about 0.193 mol) of n-butyl lithium (n-BuLi, 23%) dropwise using a cannula, the temperature was raised to room temperature and stirred for 4 hours to obtain Li-C ₅ H ₅ got

About 77 g of the bis-tertiarybutylimido-dichloro-molybdenum-dimethoxyethane ligand ( ^tBuN ) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ ) obtained in Preparation Example 1 was placed in another flame-dried 2L Schlenk flask. (0.193 mol) and diethylether (diethylether, C _-2 H ₆ O) into about 500ml, and maintained at about -10 ℃ to 0 ℃. After slowly adding Li-C ₅ H ₅ synthesized in advance thereto, the temperature was slowly raised to room temperature, and the mixture was stirred for 12 hours. After the reaction is completed, the salt generated during the reaction is removed through a filtration process, and the solvent and volatile side reactants are removed under reduced pressure to obtain a solid intermediate bis-tertiarybutylimido-cyclopentadiene-chloro-molybdenum ( ^t BuN) ₂ MoCpCl 62 g (0.183 mol) was obtained.

In another 1L Schlenk flask, the obtained intermediate and about 500ml of diethylether (diethylether, C _-2 H ₆ O) were put and maintained at about -10 ° C to 0 ° C. After slowly adding about 91.5 g (0.201 mol) of methyl lithium (MeLi, 1.6M in ether) dropwise using a cannula, the temperature was raised to room temperature and stirred for 12 hours. After the reaction was completed, salts generated during the reaction were removed through filtration, and 30 g of an orange liquid of Formula 10 (yield: 48.83%) was obtained by distilling the solvent and volatile side reactants under reduced pressure.

Density: 1.12 g/mol (at 25°C)

Boiling Point (bp) 70℃ (0.4 torr) (259.7℃ at 760mmHg)

¹ H-NMR (400 MHz, C ₆ D ₆ , 25° C.): δ 5.816 (s, 5H, MoC ₅ H ₅ ) δ 1.232 (s, 18H, (CH ₃ ) ₃ CNMo) δ 1.056 (s, 3H, _MoCH3 )

<Comparative Example 1> Tetrakis (ethylmethylamino) molybdenum (VI) Mo (NCH ₃ C ₂ H ₅ ) ₄

About 305.8 g (about 1.097 mol) of n-BuLi and about 1 L of n-hexane were put in a flame-dried 3 L Schlenk flask and then cooled to about 0°C. About 66 g (about 1.116 mol) of HN(CH ₃ )(C ₂ H ₅ ) was slowly added thereto dropwise, and then the reaction solution was slowly warmed up to room temperature and stirred for about 4 hours. Thereafter, after adding about 250 mL of THF to the flask, it was cooled to 0 ° C. MoCl ₅ (about 50 g, about 0.183 mol) dissolved in n-hexane was slowly added dropwise, and the reaction solution was stirred at room temperature for about 18 hours. . Thereafter, the reaction was stirred at reflux for an additional 2 hours to complete. After the reaction was completed, the filtrate obtained after filtering through a cellite pad and a glass frit was subjected to solvent removal under reduced pressure and distillation under reduced pressure to obtain a dark purple liquid compound represented by Comparative Example 1 below: about 16 g (yield about 27%) was obtained.

<Comparative Example 2> Bis(tert-butyl imido)bis(dimethylamino)molybdenum ( ^t BuN) ₂ Mo(N(CH ₃ ) ₂ ] ₂

Put about 1000ml of n-hexane in a flame-dried 2L Schlenk flask, slowly add about 58g (about 0.22mol) of n-butyl lithium (n-BuLi, 23%) dropwise using a cannula. The temperature is maintained between -10 and 0 °C. After slowly bubbling about 29.75 g (about 0.66 mol) of dimethylamine (C ₂ H ₆ N), the mixture was heated to room temperature and stirred for 3 hours to obtain Li-N(CH ₃ ) ₂ .

In another flame-dried 2L Schlenk flask, about 39 g of the bis-tertiarybutylimido-dichloro-molybdenum-dimethoxyethane ligand ( ^tBuN ) ₂ MoCl ₂ (C ₄ H ₁₀ O ₂ ) obtained in Example 1 was added. (0.1 mol) and toluene (toluene, C ₇ H ₈ ) into about 500 ml and maintained at -30 ° C to -20 ° C. Here, pre-synthesized Li-N(CH ₃ ) ₂ was slowly added dropwise, and the temperature was slowly raised to 50° C., followed by stirring for 12 hours. After the reaction was completed, the salt generated during the reaction was removed through filtration, and the solvent and volatile side reactants were distilled under reduced pressure to obtain about 25 g of an orange liquid represented by Comparative Example 2 (yield: about 69.6%).

Experimental example

<Experimental Example 1> Structural analysis of molybdenum precursor compounds

In order to analyze the structure of the molybdenum precursor compounds prepared in Examples 1 to 6, ¹ H-NMR analysis was performed, and the results are shown in FIG.

<Experimental Example 2> Thermal Characterization of Molybdenum Precursor Compounds

Thermogravimetric analysis (TGA) was performed to analyze the basic thermal properties of the molybdenum precursor compounds prepared in Examples 2, 5, and 6 and Comparative Examples 1 and 2, and the results are shown in FIG. 2 .

For thermogravimetric analysis (TGA), the weight change of the molybdenum precursor compound was measured while the temperature was raised from room temperature to about 500° C. at a heating rate of about 10° C./min under a nitrogen (N ₂ ) atmosphere. Specifically, the vaporization start temperature (° C.) of the molybdenum precursor compound and TG ₅₀ (° C.), which is the temperature when the weight reduction of the molybdenum precursor compound is 50%, were measured.

In addition, the weight retention rate (WR ₅₀₀ , %) of the molybdenum precursor compounds prepared in Examples 2, 5 and 6 and Comparative Examples 1 and 2 of the present invention was evaluated in the following formula 1:

In Equation 1 above,

W ₂₅ is the initial weight (wt%) of the molybdenum precursor compound at 25 ° C,

W ₅₀₀ is the weight (wt%) of the molybdenum precursor compound at 500 °C after heating from 25 °C to 500 °C at a heating rate of 10 °C/min.

The thermogravimetric analysis (TGA) measurement results are shown in FIG. 2 and Table 1 below:

As can be seen in Figure 2, in the case of the molybdenum precursor compounds of Comparative Examples 1 and 2, thermal stability is poor, leaving a lot of residue or showing a 2-step curve due to decomposition in the middle, whereas the embodiment of the present invention It can be seen that the molybdenum precursor compounds prepared in 2, 5 and 6 show that the residue is volatilized without decomposition, and these TGA characteristics show sufficient volatility to be applied to the process using ALD.

In addition, as can be seen in Table 1, most of the molybdenum precursor compounds of Examples 2, 5 and 6 of the present invention start to vaporize at around 200 ° C, and the weight of the molybdenum precursor compound is reduced by 50%. The temperature at the time, TG ₅₀ (° C.), was about 188° C. to 235° C.

In addition, it was confirmed that the residue weight (W ₅₀₀ ) of the molybdenum precursor compound at about 500° C. was about 0 wt % to 1.3 wt %. On the other hand, in the case of the molybdenum precursor compounds of Comparative Examples 1 and 2, the residue weight (W ₅₀₀ ) at about 500 ° C is about 15% to 35% by weight, and the residue weight ( W ₅₀₀ ) was found to be significantly higher than that.

On the other hand, the molybdenum precursor compounds of Examples 2, 5 and 6 had a weight retention rate (WR ₅₀₀ ) of about 98.72% or more.

In contrast, the molybdenum precursor compounds of Comparative Examples 1 and 2 had a weight retention rate (WR ₅₀₀ ) of about 65% to 85%, and the weight retention rate (WR 500) of the molybdenum precursor compounds of Examples 2, 5 and 6 ₅₀₀ ), it can be seen that it is significantly reduced.

Therefore, the molybdenum precursor compounds of the present invention exhibit excellent volatility and can form molybdenum-containing metal films, oxide thin films, and nitride thin films, particularly in the temperature range of 300 ° C to 550 ° C, for example, 350 ° C to 550 ° C. It was confirmed that it is an excellent precursor that can be

<Experimental Example 3> Deposition characteristics of molybdenum precursor compounds with ammonia (NH ₃ )

An ALD process was performed using the molybdenum precursor compounds prepared in Examples 2 and 6. NH ₃ was used as a reaction gas to deposit the molybdenum-containing nitride thin film.

First, a molybdenum-containing nitride thin film was prepared using a silicon oxide substrate (substrate) (1000 Å) as a substrate. The silicon oxide substrate is a silicon oxide substrate from which organic substances are removed by washing the surface with acetone and distilled water (DI-Water) for the purpose of removing organic substances from the surface of the silicon oxide substrate.

In order to deposit the molybdenum-containing nitride thin film, the ALD cycle was 200 times and the temperature of the substrate was fixed at about 550°C. The molybdenum precursor compounds were put into a container made of stainless steel and heated to a temperature of about 100° C., respectively, before use. At this time, the process pressure of the reactor was set to about 1 torr, and argon (Ar) gas was flowed at a flow rate of about 200 sccm to supply the precursor compound in a gaseous state to the reaction chamber.

In order to confirm the optimized resistivity characteristics of each molybdenum-containing nitride thin film, the molybdenum precursor compound prepared in Example 2 was supplied for about 20 seconds (precursor compound supply step) → argon for about 5 seconds ( Ar) supply gas to remove molybdenum precursor compound (gas) remaining in the reactor (precursor compound purge step) → supply NH ₃ as a reaction gas for about 20 seconds (NH ₃ supply step) → about 5 A molybdenum-containing nitride thin film was formed by repeating an ALD gas supply cycle consisting of supplying argon (Ar) gas for seconds to remove NH ₃ remaining in the reactor (NH ₃ purge step) 100 times. .

On the other hand, in the case of the molybdenum precursor compound prepared in Example 6, supplying the molybdenum precursor compound for about 3 seconds in an ALD cycle (precursor compound supply step) → supplying argon (Ar) gas for about 10 seconds to the reactor Remove the molybdenum precursor compound (gas) remaining inside (precursor compound purge step) → supply NH ₃ as a reaction gas for about 20 seconds (NH ₃ supply step) → argon (Ar) gas for about 10 seconds An ALD gas supply cycle consisting of a step of removing NH ₃ remaining in the reactor by supplying (NH ₃ purge step) was repeated 100 times to form a molybdenum-containing nitride thin film.

The sheet resistivity (μΩ/sq) of the molybdenum-containing nitride thin film deposited on the silicon oxide thin film substrate was measured using a 4-Point Probe System (4PPS), and transmission electron microscopy (TEM) was used to confirm the thickness of the molybdenum-containing nitride thin film. The thickness of the molybdenum-containing nitride thin film was measured to be 90.6 Å and 320.5 Å, respectively. TEM images of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared in Examples 2 and 6 are shown in FIGS. 4 and 5, respectively.

As can be seen in FIGS. 4 and 5, it was confirmed that the surface of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared in Examples 2 and 6 was uniformly formed, and the growth rate with CVD It was confirmed that the surface was not rough and non-uniformly grown because it was difficult to control the thickness because it was not controlled, but that it was formed uniformly in atomic layer units, and it was confirmed that it would exhibit excellent film properties.

Meanwhile, the resistivity (μΩ·cm) of the molybdenum-containing thin films formed using the molybdenum precursor compounds prepared in Examples 2 and 6 was confirmed.

Specifically, the resistivity of the molybdenum-containing nitride thin film was measured at room temperature using AIT's CMT-SR1000N equipment.

The resistivity measurement results of the molybdenum-containing nitride thin film are shown in FIG. 3 .

As can be seen in FIG. 3, the resistivity values of the molybdenum-containing nitride thin films formed using the molybdenum precursor compounds prepared in Examples 2 and 6 were measured to be 587.5 μΩ cm and 503.2 μΩ cm, respectively. . This can be said to be suitable for a nitride thin film for an electrode requiring low specific resistance.

For example, the molybdenum precursor compounds of the present invention are excellent precursors that can be used for gate electrodes, diffusion barriers, or capacitor electrodes used in DRAM or NAND flash, logic devices, etc. requiring low resistivity. .

<Experimental Example 4> Deposition characteristics of molybdenum precursor compounds with ammonia (NH ₃ ) plasma

An ALD process was performed using the molybdenum precursor compounds prepared in Example 6. NH ₃ plasma was used as a reaction gas to deposit the molybdenum-containing nitride thin film.

First, a molybdenum-containing nitride thin film was prepared using a silicon oxide substrate (substrate) (1000 Å) as a substrate. The silicon oxide substrate is a silicon oxide substrate from which organic substances are removed by washing the surface with acetone and distilled water (DI-Water) for the purpose of removing organic substances from the surface of the silicon oxide substrate.

In order to deposit the molybdenum-containing nitride thin film, the ALD cycle was fixed to 100 cycles, and the temperature of the substrate was 350 °C, 400 °C, and 450 °C. The molybdenum precursor compounds were put in a container made of stainless steel and heated to a temperature of about 100°C before use. At this time, the process pressure of the reactor was set to about 1 torr, and argon (Ar) gas was flowed at a flow rate of about 200 sccm to supply the precursor compound in a gaseous state to the reaction chamber.

In order to confirm the optimized resistivity characteristics of each molybdenum-containing nitride thin film, molybdenum precursor compound supply for about 3 seconds (precursor compound supply step) → argon (Ar) gas was supplied for about 10 seconds into the reactor Remove remaining molybdenum precursor compound (gas) (precursor purge step) → expose to NH _{3 plasma for about 20 seconds (NH 3 plasma} exposure step) → supply argon (Ar) gas for about 10 seconds to reactor A step of removing the remaining NH ₃ plasma (NH ₃ plasma purge step) was performed. The NH ₃ plasma used 500 sccm and 500 W.

The sheet resistance (μΩ/sq) of the molybdenum-containing nitride thin film deposited on the silicon oxide thin film substrate was measured using a 4-Point Probe System (4PPS), and the thickness was confirmed using TEM. The thickness of the molybdenum-containing nitride thin film was measured to be 57.6 Å, 79.5 Å, and 91.8 Å at 350 ° C, 400 ° C, and 450 ° C, respectively, and the molybdenum formed using the molybdenum precursor compound prepared in Example 6. TEM images of the denium-containing nitride thin film are shown in FIGS. 6, 7 and 8, respectively.

6, 7, and 8, it was confirmed that the surface of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared in Example 6 was uniformly formed.

On the other hand, the components of the molybdenum-containing nitride thin film were confirmed at each temperature of 350 ° C, 400 ° C, and 450 ° C through Auger electron spectroscopy (AES) analysis, and the results are shown in FIGS. 9, 10, and 11 indicated respectively.

As can be seen in FIGS. 9, 10, and 11, it was confirmed that the molybdenum-containing nitride thin film prepared in Example 6 had a low carbon content of 10% or less. In addition, it was confirmed that the molybdenum-containing nitride thin film prepared in Example 6 had a molybdenum-nitrogen ratio of about 1:0.8.

Meanwhile, the resistivity (μΩ·cm) of the molybdenum-containing thin film formed using the molybdenum precursor compound prepared in Example 6 was confirmed.

Specifically, the resistivity of the molybdenum-containing nitride thin film was measured at room temperature using AIT's CMT-SR1000N equipment.

The resistivity measurement results of the molybdenum-containing nitride thin film are shown in FIG. 12 .

As can be seen in FIG. 12, the resistivity values of the molybdenum-containing nitride thin film formed using the molybdenum precursor compound prepared in Example 6 were 893.3 μΩ cm (350 ° C) and 647.5 μΩ cm (400 °C), measured at 367.8 μΩ cm (450 °C). This can be said to be suitable for a nitride thin film for an electrode requiring low specific resistance.

For example, the molybdenum precursor compounds of the present invention are excellent precursors that can be used for gate electrodes, diffusion barriers, or capacitor electrodes used in DRAM or NAND flash, logic devices, etc. requiring low specific resistance. .

Claims (23)

A molybdenum precursor compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring;
X ₁ and X ₂ are each independently selected from oxygen (O), nitrogen (N), and carbon (C).
According to claim 1,
A molybdenum precursor compound represented by Formula 2 below:
[Formula 2]

In Formula 2,
Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring.
According to claim 1,
A molybdenum precursor compound represented by Formula 3 below:
[Formula 3]

In Formula 3,
Cy ₁ and Cy ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ heterocyclic rings;
Y ₁ and Y ₂ are each independently selected from oxygen (O), nitrogen (N), and carbon (C).
According to claim 1,
A molybdenum precursor compound, which is a compound represented by one of Formulas 4 to 8:
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

, and

[Formula 8]

.
According to claim 1,
The molybdenum precursor compound is heated from room temperature to 500 ° C. at a heating rate of 10 ° C./min using thermogravimetric analysis (TGA), and the weight of the molybdenum precursor compound is reduced by 50%. TG, which is the temperature ₅₀ (° C.) is 180° C. to 300° C., a molybdenum precursor compound.
According to claim 5,
The molybdenum precursor compound has a weight retention rate (WR ₅₀₀ ) of 80% or more of the following formula 1, a molybdenum precursor compound:

In Equation 1 above,
W ₂₅ is the initial weight of the molybdenum precursor compound at 25° C.;
W ₅₀₀ is the weight of the molybdenum precursor compound at 500°C when the temperature is raised from 25°C to 500°C at a heating rate of 10°C/min.
A composition for forming a molybdenum thin film comprising the molybdenum precursor compound of claim 1.
A composition for forming a molybdenum thin film deposited using a molybdenum precursor compound represented by Formula 9 below:
[Formula 9]

In Formula 9,
R ₃ is selected from the group consisting of hydrogen, a linear or branched C ₁ -C ₆ alkyl group, and a substituted or unsubstituted C ₄ -C ₈ cyclic alkyl group.
According to claim 8,
A composition for forming a molybdenum thin film, represented by Formula 10 below:
[Formula 10]

A step of reacting a compound represented by Formula A below with a compound represented by Formula B and a compound represented by Formula C in a solvent,
Method for preparing a molybdenum precursor compound represented by Formula 1 below:
[Formula A]

In Formula A,
X _A and X _B are each independently a halogen element,
[Formula B]

[Formula C]

In Formulas B and C,
M ₁ and M ₂ are each independently an alkali metal or an alkaline earth metal;
Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring;
X ₁ and X ₂ are each independently selected from oxygen (O), nitrogen (N), and carbon (C);
[Formula 1]

In Formula 1,
Cy ₁ and Cy ₂ are each independently selected from a substituted or unsubstituted C ₃ -C ₂₀ carbocyclic ring and a substituted or unsubstituted C ₁ -C ₂₀ heterocyclic ring;
X ₁ and X ₂ are each independently selected from oxygen (O), nitrogen (N), and carbon (C).
According to claim 10,
In Formula A, X _A and X _B are each independently F, Cl, Br, or I,
In Formulas B and C, wherein M ₁ and M ₂ are each independently Li, Na, K or Mg, a method for producing a molybdenum precursor compound.
According to claim 10,
The solvent includes at least one selected from the group consisting of alkanes having 5 to 8 carbon atoms, toluene, ether, tetrahydrofuran, and mono to tetraethylene glycol dimethyl ether. Method for producing a molybdenum precursor compound.
A molybdenum-containing thin film formed using the molybdenum precursor compound of claim 1.
According to claim 13,
The molybdenum-containing thin film has a specific resistance of 600 μΩ cm or less.
According to claim 13,
The molybdenum-containing thin film is at least one selected from the group consisting of a molybdenum-containing metal film, a molybdenum-containing oxide thin film, and a molybdenum-containing nitride thin film.
A method for depositing a molybdenum-containing thin film, comprising depositing a molybdenum-containing thin film on a substrate using the molybdenum precursor compound of claim 1.
17. The method of claim 16,
The deposition is carried out by chemical vapor deposition (CVD) or atomic layer deposition (ALD) at a temperature of 300 ° C to 550 ° C, molybdenum-containing thin film deposition method.
17. The method of claim 16,
The molybdenum precursor compound is selected from the group consisting of a bubbling method, a liquid delivery system (LDS) method, a vapor flow control (VFC) method, and a bypass method. A method for depositing a molybdenum-containing thin film transferred to the substrate using one or more.
According to claim 18,
The delivery method includes a bubbling method or a bypass method of vaporizing by heating,
The bubbling method is performed using a carrier gas in a temperature range of 0.1 to 10 torr and 100 ° C to 150 ° C,
The bypass method of vaporizing by heating is performed using a vapor pressure of 0.1 to 1.5 torr in a temperature range of room temperature to 100 ° C., a method for depositing a molybdenum-containing thin film.
17. The method of claim 16,
A method of depositing a molybdenum-containing thin film using thermal energy or plasma or applying a bias on a substrate during the deposition.
17. The method of claim 16,
The molybdenum-containing thin film includes a molybdenum-containing metal film,
In the deposition, a method of depositing a molybdenum-containing thin film using a reaction gas containing at least one selected from the group consisting of hydrogen (H ₂ ), nitrogen (N ₂ ), and ammonia (NH ₃ ).
17. The method of claim 16,
The molybdenum-containing thin film includes a molybdenum-containing oxide thin film,
During the deposition, water vapor (H ₂ O), oxygen (O ₂ ), oxygen plasma (O ₂ Plasma), nitrogen oxide (NO, N ₂ O), nitrogen oxide plasma (N ₂ O Plasma), oxygen nitride (N ₂ A method for depositing a molybdenum-containing thin film using a reactive gas containing at least one selected from the group consisting of O ₂ ), hydrogen peroxide (H ₂ O ₂ ), and ozone (O ₃ ).
17. The method of claim 16,
The molybdenum-containing thin film includes a molybdenum-containing nitride thin film,
During the deposition, a reaction gas containing at least one selected from the group consisting of ammonia (NH ₃ ), ammonia plasma (NH ₃ Plasma), hydrazine (N ₂ H ₄ ), and nitrogen plasma (N ₂ Plasma) is used. A method for depositing a molybdenum-containing thin film.

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