KR20210058289A - Tungsten Precursor, Method for Preparation of the Same, and Tungsten-Containing Thin Film, Method of Manufacturing the Same - Google Patents

Abstract

The present invention relates to a tungsten precursor, a manufacturing method thereof, a tungsten-containing thin film using the same, and a manufacturing method thereof. By using the tungsten precursor including a compound represented by chemical formula 1, it is possible to manufacture a high-quality tungsten-containing thin film with high durability and purity at low cost.

Description

Tungsten Precursor, Method for Preparation of the Same, and Tungsten-Containing Thin Film, Method of Manufacturing the Same}

The present invention relates to a tungsten precursor, a method for manufacturing the same, and a method for manufacturing a tungsten-containing thin film using the same, and more particularly, a tungsten precursor that can be usefully used as a tungsten precursor, a method for manufacturing the tungsten precursor, and a tungsten-containing thin film using the tungsten precursor, and It relates to a method of manufacturing the same.

In the rapidly developing information society, a highly integrated device device with a high data transmission speed is required to process a large amount of information more quickly, but it is a reality that it is difficult to secure the characteristics of the desired device device due to the high integration of the device device. .

In other words, as the degree of integration of memory and non-memory device devices increases and the structure becomes increasingly complex, high aspect ratio and excellent step coverage of thin films are evaluated as important process factors, but conventional physical vapor deposition methods (PVD) has a disadvantage of very poor step coverage due to its process characteristics.

Therefore, it is very difficult to form a thin film with a uniform thickness on a fine and curved pattern by a conventional physical vapor deposition method. That is, since the area where the thin film is to be formed is generally a fine and curved pattern or a surface of a contact hole, it is practically very difficult to apply the physical vapor deposition process.

As an alternative to the conventional physical vapor deposition method, a widely used thin film manufacturing method is an organometallic chemical vapor deposition (CVD) method using a volatile organometallic compound. In the CVD method, an organometallic compound vaporized by various methods, such as bubbling by a carrier gas or vaporizing an injected liquid fuel with a vaporizer, is adsorbed on a heated substrate and then decomposed. It is the principle of deposition.

These chemical vapor deposition methods are replacing the existing physical vapor deposition methods such as sputtering and thermal evaporation because they have a high aspect ratio and excellent step coverage, which are essential for highly integrated devices. In order to obtain coverage, an original layer deposition method (ALD) is applied.

Atomic layer deposition (ALD) is a method of depositing an atomic layer on a semiconductor substrate by sequentially injecting and removing a reactant into the chamber. This atomic layer deposition method is a deposition method that uses a chemical reaction like chemical vapor deposition (CVD), but it is distinguished from chemical vapor deposition in that each gas is injected at the same time so that each gas is not mixed in the chamber and flows in a pulse form. do.

In the chemical vapor deposition method or atomic layer deposition method, conditions that the compound must have include high thermal stability, high volatility, low toxicity, chemical stability, and liquid at room temperature. In addition, there should be no side reactions that spontaneously decompose or react with other substances in the process of vaporization and transfer to the gas phase. In particular, in the case of atomic layer deposition, reaction with special reaction gases should be easy.

In addition, tungsten-containing thin films, especially tungsten nitride films, have low resistance, excellent adhesion, and excellent diffusion barrier properties, so they can be used as good barriers to prevent diffusion of copper in microelectronic circuits, wiring materials, or electrodes for capacitors and transistors. In addition, a representative compound used to form such a tungsten-containing thin film is tungsten hexafluoride (WF ₆ ). In this case _{, the formation of a tungsten-containing thin film using WF 6} -NH ₃ or the like is disclosed in Korean Patent Laid-Open Publication No. 10-2005-0087428, but HF, a by-product after the reaction from _{WF 6} and NH _{3 , is Si or SiO 2} There is a drawback of being able to attack the substrate made of, and also, unwanted by-products of ammonium fluoride are generated. In addition, the deposited tungsten nitride film has a polycrystalline structure with a large number of grain boundaries, which can cause damage to the diffusion barrier properties, which can lead to serious loss of manufacturing yield and reliability problems during the semiconductor device process. Have.

To solve this problem, a method of forming a tungsten-containing thin film using a halogen-free amide-based compound is described in Chemistry of Materials, 2003, 15, 2969-2976 and Journal of The Electrochemical Society, 150(10), C740. -C744 (2003) discloses bis(tertbutylimido)bis(dimethylamino)tungsten {(tBuN) ₂ W(NMe ₂ ) ₂ } as a representative compound of the tungsten amide series, but this is tungsten by imido ligand. Due to the high stability due to the π-bonding between the central metal and nitrogen, the ligand decomposition in the process does not occur cleanly, so carbon contamination is very severe. In addition, a method of forming a tungsten-containing thin film using a tungsten compound into which a cyclopentadienyl ligand was introduced was also disclosed in Surface & Coatings Technology, 201, 9120-9124 (2007), but its specific compound, diisopropylcyclopentadienyl diene Hydro tungsten (iPrCp) ₂ WH ₂ has a very low vapor pressure and low deposition rate.

Accordingly, the present inventors provide a tungsten precursor having high thermal stability, high volatility, low toxicity, and chemical stability, and a method for manufacturing the same as a solution to the above problems. By using the tungsten precursor, it is thermally stable, It is intended to provide a highly reliable tungsten-containing thin film.

Korean Patent Application Publication No. 10-2005-0087428

Chemistry of Matererials, 2003,15,2969-2976 Journal of The Electrochemical Society,150(10), C740-C744 (2003) Surface & Coatings Technology, 201, 9120-9124 (2007)

An object of the present invention is to provide a tungsten precursor having high thermal stability and high volatility, a method of manufacturing the same, and a method of manufacturing a tungsten-containing thin film having excellent high purity and durability using the tungsten precursor.

The tungsten precursor according to the present invention includes a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ to R ₆ are each independently a hydrogen atom or a C1-C5 alkyl group, provided that R ₁ Except when to R ₆ is a hydrogen atom at the same time;

The alkyl group is a halogen atom, trifluoromethyl group, amino group, cyano group, hydroxy, C1-C10 alkyl group, C1-C10 alkoxy group, C3-C12 cycloalkyl group, C3-C12 heterocycloalkyl group, C6-C20 May be further substituted with one or more substituents selected from the aryl group of and C3-C20 heteroaryl group;

은 단일결합 또는 이중결합이다.remind

Is a single bond or a double bond.

According to an embodiment of the present invention, the compound represented by Formula 1 may be any one of the compounds represented by the following structure.

The compound represented by Formula 1 may be prepared by reacting a compound represented by the following Formula 2 with a compound represented by the following Formula 3, and then reacting with a compound represented by the following Formula 4.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 1]

In this case, in Chemical Formulas 1 to 4,

M is lithium (Li), sodium (Na) or potassium (K);

X is halogen;

R is a C1-C2 alkyl group;

R ₁ to R ₆ are each independently a hydrogen atom or a C1-C5 alkyl group, provided that R ₁ Except when to R ₆ is a hydrogen atom at the same time;

The alkyl group is a halogen atom, trifluoromethyl group, amino group, cyano group, hydroxy, C1-C10 alkyl group, C1-C10 alkoxy group, C3-C12 cycloalkyl group, C3-C12 heterocycloalkyl group, C6-C20 May be further substituted with one or more substituents selected from the aryl group of and C3-C20 heteroaryl group;

은 단일결합 또는 이중결합이다.remind

Is a single bond or a double bond.

In addition, the step of preparing the compound represented by Formula 1 may be performing the reaction at 15 to 60°C for 12 to 24 hours.

In addition, the tungsten-containing thin film according to the present invention is manufactured using the tungsten precursor, and the manufacturing method includes depositing the tungsten precursor on a substrate, and the deposition is performed by plasma chemical vapor deposition. ) Process, thermal chemical vapor deposition process, plasma atomic layer deposition (plasma ALD, PEALD) or thermal atomic layer deposition (Thermal ALD). At this time, the substrate to be deposited is not limited to a silicon wafer for semiconductor processing, and a flat plate composed of plastic, glass, metal, metal oxide, metal nitride, metal carbide, metal carbonitride, other ceramic material, silica, carbon, or Including those with a three-dimensional structure.

In addition, the depositing step may be performed under the condition that the temperature of the substrate is 100 to 450°C.

Further, the cycle of the deposition process may be repeatedly performed until the desired thickness of the tungsten-containing thin film is achieved.

In addition, the method of manufacturing the tungsten-containing thin film is performed by an atomic layer deposition method,

1) carrying a substrate into the reaction chamber and maintaining the sintering temperature;

2) a pretreatment purging step of injecting a purging gas into the reaction chamber;

3) supplying the tungsten compound onto the substrate into the reaction chamber;

4) a first purging step of supplying a purging gas into the reaction chamber to leave only the tungsten compound chemically adsorbed on the substrate and remove the physisorbed tungsten compound;

5) supplying a reaction gas into the reaction chamber to react with the chemically adsorbed tungsten compound layer;

6) a second purging step of discharging by-products and unreacted substances generated by the reaction of the chemically adsorbed tungsten compound layer and the reaction gas to the outside of the reaction chamber

It may include.

In addition, in the first purging step and the second purging step _{, at least one selected from helium (He), hydrogen (H 2} ), nitrogen (N ₂ ), argon (Ar) and ammonia (NH ₃ ) is injected into the reaction chamber. And, the gas present in the reaction chamber may be discharged to the outside using a vacuum pump.

The tungsten precursor according to the present invention has the advantage of high volatility and excellent thermal stability because it has a liquid or low melting point at room temperature.

In addition, the tungsten precursor according to the present invention is very economical because it can be manufactured through a simple process.

Since the tungsten precursor according to the present invention has high thermal stability and high volatility, a thin film manufactured using the tungsten precursor may have high purity and durability.

^{1 is a 1} H-NMR result of (2-methylallyl) (ethylcyclopentadienyl) (dicarbonyl) tungsten prepared in Example 1.
2 is a thermogravimetric analysis (TGA) result of (2-methylallyl) (ethylcyclopentadienyl) (dicarbonyl) tungsten prepared in Example 1. FIG.
3 is a result of measuring the vapor pressure of (2-methylallyl) (ethylcyclopentadienyl) (dicarbonyl) tungsten prepared in Example 1.
4 is a diagram showing a method of depositing a tungsten-containing thin film prepared in Example 2.
5 is a result of measuring the deposition rate and sheet resistance of the tungsten-containing thin film prepared in Example 2.
6 is an image observed with a scanning electron microscope (SEM) observing the thickness of the tungsten-containing thin film prepared in Example 2. FIG.
7 is a graph showing a composition change according to the depth of the tungsten-containing thin film prepared in Example 2.

The tungsten precursor according to the present invention includes a compound represented by the following formula (1), has a liquid or low melting point at room temperature, has high volatility, and excellent thermal stability.

[Formula 1]

In Formula 1,

R ₁ to R ₆ are each independently a hydrogen atom or a C1-C5 alkyl group, provided that R ₁ Except when to R ₆ is a hydrogen atom at the same time;

The alkyl group is a halogen atom, trifluoromethyl group, amino group, cyano group, hydroxy, C1-C10 alkyl group, C1-C10 alkoxy group, C3-C12 cycloalkyl group, C3-C12 heterocycloalkyl group, C6-C20 May be further substituted with one or more substituents selected from the aryl group of and C3-C20 heteroaryl group;

은 단일결합 또는 이중결합이다.remind

Is a single bond or a double bond.

In the present specification, the term "alkyl group" refers to a linear or branched saturated hydrocarbon group, and includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, or heptyl. The C1-C5 alkyl group refers to an alkyl group having an alkyl unit having 1 to 5 carbon atoms, and when alkyl is substituted, the number of carbon atoms of the substituent is not included.

In the present specification, the term "halogen atom" refers to a halogen element, and includes, for example, fluoro, chloro, bromo, and iodo.

The tungsten precursor represented by Chemical Formula 1 is liquid at room temperature or has a low melting point and is highly volatile, so it is very economical to deposit a thin film at a low temperature when forming a tungsten-containing thin film.

In addition, the tungsten precursor represented by Formula 1 according to the present invention has a low melting point or liquid properties, preferably the R ₁ to R ₆ May be independently a hydrogen atom or a C1-C5 alkyl group, and the alkyl group may be further substituted with a C1-C5 alkyl group or a C1-C5 alkoxy, in terms of having a high vapor pressure and thus an excellent thin film deposition rate. More preferably, it may be a tungsten precursor represented by the following structure, but is not limited thereto.

The compound represented by Formula 1 may be prepared by reacting a compound represented by the following Formula 2 with a compound represented by the following Formula 3, and then reacting with the compound represented by the following Formula 4.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 1]

In this case, in Chemical Formulas 1 to 4,

M is lithium (Li), sodium (Na) or potassium (K);

X is halogen;

R is a C1-C2 alkyl group;

R ₁ to R ₆ are each independently a hydrogen atom or a C1-C5 alkyl group, provided that R ₁ Except when to R ₆ is a hydrogen atom at the same time;

The alkyl group is a halogen atom, trifluoromethyl group, amino group, cyano group, hydroxy, C1-C10 alkyl group, C1-C10 alkoxy group, C3-C12 cycloalkyl group, C3-C12 heterocycloalkyl group, C6-C20 May be further substituted with one or more substituents selected from the aryl group of and C3-C20 heteroaryl group;

은 단일결합 또는 이중결합이다.remind

Is a single bond or a double bond.

The method of manufacturing the tungsten precursor according to the present invention is very effective because it can produce a high-purity tungsten precursor with a high yield through a very simple process.

The method of preparing the tungsten precursor may be performed at 15 to 60° C. for 12 to 24 hours. At this time, with respect to 1 mole of the compound represented by Formula 2, 7 to 10 moles of the compound represented by Formula 3 were used to react under a reaction solvent, and a compound represented by the following Formula 4 was added to the compound represented by Formula 2. With respect to 1 mole of the compound, it can be reacted using 1 to 1.2 moles.

At this time, the reaction solvent may be any solvent that does not react with the starting material among ordinary organic solvents. For example, normal hexane (n-Hexane), cyclohexane (Cyclohexane), normal pentane (n-Pentane), diethyl ether One or more selected from the group consisting of (Ether), toluene, tetrahydrofuran (THF), acetonitrile, and propionitrile may be selected.

The present invention provides a tungsten-containing composition for thin film deposition comprising a tungsten precursor represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ to R ₆ are each independently a hydrogen atom or a C1-C5 alkyl group, provided that R ₁ Except when to R ₆ is a hydrogen atom at the same time;

The alkyl group is a halogen atom, trifluoromethyl group, amino group, cyano group, hydroxy, C1-C10 alkyl group, C1-C10 alkoxy group, C3-C12 cycloalkyl group, C3-C12 heterocycloalkyl group, C6-C20 May be further substituted with one or more substituents selected from the aryl group of and C3-C20 heteroaryl group;

은 단일결합 또는 이중결합이다.remind

Is a single bond or a double bond.

The tungsten precursor is also very stable thermally, and a tungsten-containing thin film manufactured using a thin film deposition composition containing a tungsten precursor has the advantage of excellent mechanical properties and excellent thermal stability.

In addition, the tungsten precursor may be deposited by adjusting the content within a range that can be recognized by a person skilled in the art in consideration of the deposition condition of the thin film, the thickness of the thin film, or the characteristics of the thin film.

The tungsten-containing thin film according to the present invention may be manufactured using the tungsten precursor. The tungsten-containing thin film of the present invention can be manufactured by a conventional method, and specific examples include organometallic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), low pressure vapor deposition (LPCVD), plasma enhanced vapor deposition (PECVD), or It may be manufactured by plasma enhanced atomic layer deposition (PEALD).

In the method of manufacturing the tungsten-containing thin film, the injection temperature of the tungsten precursor may be 60 to 120°C, preferably 80 to 100°C.

In addition, due to the high volatility of the tungsten precursor, the deposition of a thin film may be performed at a lower temperature, such as 100° C. to 450° C., and preferably 300 to 400° C. of the substrate on which the tungsten precursor is to be deposited. In addition, the pressure inside the chamber may be adjusted to 0.1 to 5 torr.

In addition, the reaction gas used in the method of manufacturing the thin film is not limited, but hydrogen (H ₂ ), hydrazine (N ₂ H ₄ ), ozone (O ₃ ), ammonia (NH ₃ ), nitrogen (N ₂ ) , Silane (SiH ₄ ), borane (BH ₃ ), diborane (B ₂ H ₆ ) and phosphine (PH ₃ ) one or more mixed gases selected from may be used, and the reaction gas is 10 to 10,000 sccm It is preferably supplied at a flow rate of, and more preferably, it may be supplied at a flow rate of 500 to 2,000 sccm.

In the method of manufacturing the thin film, the cycle may be repeatedly performed until the desired thickness of the thin film is achieved.

The present invention provides a tungsten-containing thin film manufactured using the tungsten precursor, and the tungsten-containing thin film manufactured by the above manufacturing method uses a tungsten-containing composition including a tungsten precursor having high volatility and high thermal stability. , It can provide a thin film having very excellent electrical and chemical properties, and can have high purity, high deposition rate, and excellent durability despite deposition at a low substrate temperature.

Hereinafter, the present invention will be described in more detail through examples. Prior to this, terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention. Accordingly, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention, and do not represent all the technical ideas of the present invention. It should be understood that there are various equivalents and variations.

[Example 1] Preparation of (2-methylallyl) (ethylcyclopentadienyl) (dicarbonyl) tungsten synthesis [(EtCp)(C ₄ H ₇ )W(CO) ₂ ]

To a flame-dried 1000 ml Schlenk flask, tricarbonyltripropionitrile tungsten 100 g (0.231 mol, 1.00 equivalent) and propionitrile 500 ml were added under a nitrogen atmosphere, and 3-chloro-2-methylpropene was added at 25°C. It was added slowly at. The reaction solution was stirred at 25 DEG C for 12 hours, concentrated under reduced pressure, and then 500 ml of diethyl ether was added. Thereafter, the precipitated yellow-brown solid compound was filtered to obtain a solid compound. 100 g (0.227 mol, 1.00 equivalent) of the obtained yellow-brown solid compound and 22.77 g (0.227 mol, 1.00 equivalent) of lithium ethylcyclopentadienyl were added, and 300 ml of tetrahydrofuran was added. The reaction solution was stirred at 25° C. for 18 hours, then reduced pressure to remove the solvent, and 300 ml of hexane was added. After stirring at 25° C. for 1 hour, lithium chloride (LiCl) produced as a by-product was filtered, and the filtrate was vacuumed to remove the solvent, and distilled under reduced pressure (100° C., 0.5 ㎜Hg), and the title compound was 70 g ( Yield 70%) was obtained. The specific peak of ¹ H NMR of the product is as follows.

¹ H NMR (C ₆ D ₆ ): δ 4.56 (7H, s), 2.79 (2H, s), 2.28 (3H, s), 1.86 (2H, q), 1.41 (2H, s), 0.82 (3H, t)

^{1 shows 1} H-NMR of (2-methylallyl) (ethylcyclopentadienyl) (dicarbonyl) tungsten synthesis [(EtCp)(C ₄ H ₇ )W(CO) ₂ ] prepared by the above method. As a result, it can be seen that (2-methylallyl)(ethylcyclopentadienyl)(dicarbonyl)tungsten synthesis [(EtCp)(C ₄ H ₇ )W(CO) ₂ ] was prepared. Figure 2 shows the thermogravimetric analysis of (2-methylallyl) (ethylcyclopentadienyl) (dicarbonyl) tungsten synthesis [(EtCp)(C ₄ H ₇ )W(CO) ₂ ] prepared by the above method ( TGA), it was possible to confirm high volatility and high thermal stability.

In addition, vapor pressure curve of (2-methylallyl) (ethylcyclopentadienyl) (dicarbonyl) tungsten [(EtCp)(C ₄ H ₇ )W(CO) _{2] prepared by the above method in FIG. 3} From, it was confirmed that the vapor pressure of the tungsten precursor prepared by the above method was high.

[Example 2] Preparation of Tungsten-Containing Thin Film

A tungsten-containing thin film was formed by depositing Example 1, which is a tungsten precursor in a vapor state, on a substrate at a temperature of 385° C. on a silicon substrate by atomic layer deposition. Ammonia (NH ₃ ) was used as the reaction gas, and argon, an inert gas, was used for purge purposes.

4 and Table 1 show a deposition method for a specific tungsten-containing thin film.

Board
Temperature
(℃) Precursor temperature
(℃) Precursor
Injection time
(sec) Chamber pressure
(torr) Fudge Reaction gas injection Fudge deposition
Count
(cycle) flux
(sccm) time
(sec) flux
(sccm) time
(sec) flux
(sccm) time
(sec) 385 90 13 0.5torr 1000 10 1500 20 1000 15 300

6 is a scanning electron microscope (SEM) image of a tungsten-containing thin film deposited on a silicon substrate according to Example 2. The thickness of the thin film prepared by the above method was observed to be 300 Å, the deposition rate of the tungsten-containing thin film deposited on the silicon substrate according to Example 2 was 1.0 Å/cycle, and it was confirmed that the sheet resistance was 350 Ω/□. (See Fig. 5).

In addition, as a result of analyzing the composition change according to the depth of the thin film deposited on the silicon substrate according to Example 2 by using Auger Electron Spectroscopy (AES), the tungsten nitride thin film was 46% tungsten and 37% nitrogen. , Was observed to have a composition of 9% carbon and 8% oxygen (see Fig. 7).

As described above, when the tungsten precursor according to the present invention is used, it can be seen that a high-purity tungsten-containing thin film having a low sheet resistance of 350 Ω/□ and a high deposition rate of 1.0 Å/cycle can be manufactured.

Claims (12)

A tungsten precursor comprising a compound represented by the following formula (1).

[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently a hydrogen atom or a C1-C5 alkyl group, provided that R ₁ Except when to R ₆ is a hydrogen atom at the same time;
The alkyl group is a halogen atom, trifluoromethyl group, amino group, cyano group, hydroxy, C1-C10 alkyl group, C1-C10 alkoxy group, C3-C12 cycloalkyl group, C3-C12 heterocycloalkyl group, C6-C20 May be further substituted with one or more substituents selected from the aryl group of and C3-C20 heteroaryl group;
remind

Is a single bond or a double bond.
The method of claim 1,
The tungsten precursor, characterized in that the R ₁ to R ₆ are each independently a hydrogen atom or a C1-C4 alkyl group.
The method of claim 2,
Formula 1 is a tungsten precursor, characterized in that any one of the compounds represented by the following structure.

After reacting a compound represented by the following formula (2) with a compound represented by the following formula (3), reacting with a compound represented by the following formula (4) to prepare a compound represented by the following formula (1) A method for producing a tungsten precursor containing a compound represented by.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 1]

In this case, in Chemical Formulas 1 to 4,
M is lithium (Li), sodium (Na) or potassium (K);
X is halogen;
R is a C1-C2 alkyl group;
The R ₁ to R ₆ are each independently a hydrogen atom or a C1-C5 alkyl group, provided that R ₁ Except when to R ₆ is a hydrogen atom at the same time;
The alkyl group is a halogen atom, trifluoromethyl group, amino group, cyano group, hydroxy, C1-C10 alkyl group, C1-C10 alkoxy group, C3-C12 cycloalkyl group, C3-C12 heterocycloalkyl group, C6-C20 May be further substituted with one or more substituents selected from the aryl group of and C3-C20 heteroaryl group;
remind

Is a single bond or a double bond.
The method of claim 4,
The step of preparing the compound represented by Formula 1 is a method of producing a tungsten precursor, characterized in that the reaction is performed at 15 to 60° C. for 12 to 24 hours.
A tungsten-containing thin film manufactured using the tungsten precursor according to claim 1.
As a method of manufacturing a tungsten-containing thin film according to claim 6,
And depositing the tungsten precursor on a substrate, wherein the deposition includes a plasma chemical vapor deposition process, a thermal chemical vapor deposition process, and a plasma atomic layer deposition (plasma ALD, PEALD). ) Or thermal atomic layer deposition (Thermal ALD).
The method of claim 7,
The depositing step is a method of manufacturing a tungsten-containing thin film, characterized in that it is performed under a condition in which the temperature of the substrate is 100 to 450°C.
The method of claim 7,
A method of manufacturing a tungsten-containing thin film, characterized in that the cycle of the deposition process is repeatedly performed until the desired thickness of the tungsten-containing thin film is achieved.
The method of claim 7,
The method of manufacturing the tungsten-containing thin film is performed by an atomic layer deposition method,
1) carrying a substrate into the reaction chamber and maintaining the sintering temperature;
2) a pretreatment purging step of injecting a purging gas into the reaction chamber;
3) supplying the tungsten compound onto the substrate into the reaction chamber;
4) a first purging step of supplying a purging gas into the reaction chamber to leave only the tungsten compound chemically adsorbed on the substrate, and to remove the physisorbed tungsten compound;
5) supplying a reaction gas into the reaction chamber to react with the chemically adsorbed tungsten compound layer;
6) a second purging step of discharging by-products and unreacted substances generated by the reaction of the chemically adsorbed tungsten compound layer and the reaction gas to the outside of the reaction chamber
Method for producing a tung step thin film comprising a
The method of claim 10,
In the first purging step and the second purging step _{, at least one selected from helium (He), hydrogen (H 2} ), nitrogen (N ₂ ), argon (Ar) and ammonia (NH ₃ ) is injected into the reaction chamber, A method of manufacturing a tungsten-containing thin film, characterized in that the gas present in the reaction chamber is discharged to the outside by using a vacuum pump.
The method of claim 7,
In the depositing step, the substrate may be any one of a wafer, plastic, glass, metal, metal oxide, metal nitride, metal carbide, metal carbonitride, ceramic material, silica, or a material having a three-dimensional structure consisting of carbon. Method for producing a tungsten-containing thin film as described above.

Images