Method for producing molybdenum dioxydichloride

Abstract

The present invention relates to a method for producing molybdenum dioxide dichloride. The method for producing molybdenum dioxide dichloride of the present invention can produce molybdenum dioxide dichloride in high yield and without using hazardous chlorine gas or high reaction temperatures, and therefore has the advantages of being safe and being capable of being produced in both small-scale and large-scale production, making it an industrially very useful and efficient method.

Description

Technical Field

[0001] The present invention relates to a method for producing molybdenum dioxydichloride (MoO2Cl2). More specifically, it relates to a method for synthesizing anhydrous and solvent-free molybdenum dioxydichloride.

Background Art

[0002] Molybdenum dioxydichloride (MoO2Cl2) is a well-known molybdenum inorganic compound.

[0003] Recently, the molybdenum dioxydichloride (MoO2Cl2) has attracted attention as a precursor for the deposition of metal molybdenum films (CVD or ALD) through vacuum deposition technology in the semiconductor industry.

[0004] The molybdenum film deposited using the molybdenum dioxydichloride (MoO2Cl2) generally exhibits better performance compared to that deposited using an organometallic molybdenum precursor. The reason is that molybdenum dioxydichloride (MoO2Cl2) does not contain nitrogen and carbon atoms, so the purity of the final film is higher.

[0005] In addition, the two most common methods for synthesizing the molybdenum dioxydichloride (MoO2Cl2) are chlorinating molybdenum dioxide (MoO2) and molybdenum trioxide (MoO3) as shown in Chemical Formula 1 and Chemical Formula 2 below.

[0006] MoO2 + Cl2 → MoO2Cl2 (Chemical Formula 1)

[0007] 2MoO3 + 2Cl2 → 2MoO2Cl2 + O2 (Chemical Formula 2)

[0008] The two methods described above, Chemical Formula 1 and Chemical Formula 2, involve passing an excess amount of chlorine gas through the solid oxide layers of Chemical Formula 1 and Chemical Formula 2, namely molybdenum dioxide (MoO2) and molybdenum trioxide (MoO3), at high temperatures. In this process, the passage of chlorine gas proceeds at temperatures of 200°C or higher through the molybdenum dioxide layer and at 900°C or higher through the molybdenum trioxide layer.

[0009] In the chemical formulas 1 and 2 described above, the molybdenum dioxydichloride (MoO2Cl2) produced by passing chlorine gas through the solution is separated and obtained by sublimation.

[0010] However, the two manufacturing methods for chemical formulas 1 and 2 described above are (i) There is a problem in that the excess chlorine gas used in the manufacturing process must be removed, (ii) Molybdenum dioxydichloride (MoO2Cl2) obtained by sublimation sublimes into a very light and fluffy solid, which occupies the acquisition space and has a high potential to block the exhaust line.

[0011] To address the aforementioned problems, other methods for producing molybdenum dioxydichloride (MoO2Cl2) have been proposed, such as those shown in chemical formulas 3-1 and 3-2 below.

[0012] Na2MoO4+4Me3SiCl(in dme)→MoO2Cl2(dme)+2NaCl+2(Me3Si)2O (chemical formula 3-1)

[0013] (NH4)2Mo2O7+6Me3SiCl(in dme)→2MoO2Cl2(dme)+2NH4Cl+3(Me3Si)2O (chemical formula 3-2)

[0014] The production methods for chemical formulas 3-1 and 3-2 involve reacting sodium molybdenum dioxydichloride (Na2MoO4) and ammonium molybdate ((NH4)2Mo2O7) with chlorotrimethylsilanedimethoxyethane (Me3SiCl(in dme)) to produce molybdenum dioxydichloride solvated adduct (MoO2Cl2(dme)), which is the solvated form of 1,2-dimethoxyethane (dme) of molybdenum dioxydichloride.

[0015] Both methods, described above using chemical formulas 3-1 and 3-2, can yield pure molybdenum dioxydichloride dimethoxyethane (MoO2Cl2(dme)) in high yield, and this product is widely used as an intermediate for the synthesis of many molybdenum compounds.

[0016] While it is known that the solvent can be removed from the aforementioned solvated adducts using common techniques (e.g., heating under vacuum), when molybdenum dioxydichloride dimethoxyethane (MoO2Cl2(dme)) is heated above its melting point, the molybdenum dioxydichloride decomposes, making it impossible to obtain pure molybdenum dioxydichloride without the solvent.

[0017] Furthermore, other methods for producing molybdenum dioxydichloride (MoO2Cl2) are disclosed in the following chemical formula 4.

[0018] MoOCl4+(Me3Si)2O→MoO2Cl2+2Me3SiCl (chemical formula 4)

[0019] Perchlorinated molybdenum oxytetrachloride (MoOCl4) is converted in high yield to the preferred molybdenum dioxydichloride (MoO2Cl2) through reaction with hexamethyldisiloxane. However, molybdenum oxytetrachloride (MoOCl4) as the starting material in the above chemical formula 4 is not readily available.

[0020] As described above, there are many problems in the production of molybdenum dioxydichloride (MoO₂Cl₂), and it is urgent to develop a new production method for molybdenum dioxydichloride (MoO₂Cl₂) to improve this situation.

Summary of the Invention

Problems to be Solved by the Invention

[0021] The present invention aims to provide a method for producing molybdenum dioxydichloride (MoO₂Cl₂) that overcomes the disadvantages of the conventional known production methods while providing various advantages.

[0022] In addition to the above - stated clear objectives, the present invention can also aim to achieve other objectives that can be easily derived by a person of ordinary skill in the art from such objectives and the overall technology of this specification.

Means for Solving the Problems

[0023] The method for producing molybdenum dioxydichloride (MoO₂Cl₂) of the present invention for the above - mentioned purpose can be expressed as shown in Chemical Formula 5 below.

[0024] MoO₃ + SOCl₂ → MoO₂Cl₂ + 2SO₂ (Chemical Formula 5)

[0025] Specifically, the method for producing molybdenum dioxydichloride (MoO₂Cl₂) of the present invention (i) A step of mixing molybdenum trioxide anhydrous and thionyl chloride in a solvent under an inert gas to produce a mixture (the first step of mixture production); (ii) A step of raising the temperature of the produced mixture under an inert gas and refluxing and stirring to produce a precipitated solid product (the second step of solid product production); and (iii) A step of separating and purifying molybdenum dioxydichloride (MoO₂Cl₂) from the produced solid product (the third step of separation and purification of molybdenum dioxydichloride (MoO₂Cl₂)); is included.

[0026] Looking at each of the above steps, In the first stage of the mixture generation, the ratio (mole) of the usage amount of molybdenum trioxide to thionyl chloride may be 1:0.5 to less than 1:2.0.

[0027] The solvent in the first stage of the mixture generation must be a non-coordinating solvent that does not react or coordinate with the product molybdenum dioxydichloride (MoO₂Cl₂).

[0028] Specifically, the non-coordinating solvent may be an aliphatic and aromatic solvent having 2 or more carbon atoms and containing a halogen element.

[0029] The solvent may have a boiling point of 50°C to 200°C.

[0030] The inert gas in the reaction vessel in the first stage of the mixture generation and the second stage of the solid product generation may be one or more of the gases selected from the group consisting of nitrogen (N₂), argon (Ar), and helium (He).

[0031] In the second stage of the solid product generation, the rising temperature for reflux stirring may be 50°C to 200°C.

[0032] In the third stage of the separation and purification of the molybdenum dioxydichloride (MoO₂Cl₂), the separation is a step of filtering the generated solid product, washing it with the solvent in the first stage of the mixture generation, and drying it under vacuum to obtain molybdenum dioxydichloride (MoO₂Cl₂). <000后記各段階を見ると、

[0033] The purification is performed by a method of sublimating the molybdenum dioxydichloride (MoO₂Cl₂) obtained by the drying.

Advantages of the Invention

[0034] As described above, the present invention's method for producing molybdenum dioxydichloride (MoO2Cl2) differs from conventional known techniques in that it avoids the use of dangerous chlorine gas and high reaction temperatures, and has the advantage of being able to produce solvent-free molybdenum dioxydichloride (MoO2Cl2) in high yield.

[0035] Furthermore, the method for producing molybdenum dioxydichloride (MoO2Cl2) according to the present invention is safe because it does not use hazardous chlorine gas or high reaction temperatures, and it has the advantage of being suitable for both small-scale and large-scale production.

[0036] Furthermore, since it uses molybdenum trioxide (MoO3) and thionyl chloride (SOCl2), which are readily available and inexpensive, as reactants, it has the advantage of being economical in the production of molybdenum dioxydichloride (MoO2Cl2). [Brief explanation of the drawing]

[0037] [Figure 1] This graph shows the TGA (Thermogravimetric Analyzer) analysis results for purified molybdenum dioxydichloride (MoO2Cl2) obtained according to Example 1 of the present invention (Example 1) and molybdenum dioxydichloride (MoO2Cl2) purchased from Sigma Aldrich (Reference). [Figure 2] This shows the results of ICP-MS (Inductively Coupled Plasma Mass Spectrometer) analysis of sublimated molybdenum dioxydichloride (MoO2Cl2) according to the present invention. [Best Mode for Carrying Out the Invention]

[0038] The present invention will be described in detail below.

[0039] However, the following description is merely illustrative and detailed to illustrate specific embodiments, and the present invention can be modified in many ways and take various forms; therefore, the present invention is not limited to the specific embodiments illustrated. The present invention should be understood to include all modifications, equivalents, or substitutions that fall within the spirit and technical scope of the present invention.

[0040] Furthermore, although the following description includes many specific details such as concrete components, these are provided solely to aid in a more general understanding of the present invention, and it will be obvious to those with ordinary skill in the art that the present invention can be implemented even without such details.

[0041] Furthermore, when describing the present invention, if it is determined that a specific description of a related known function or configuration may unnecessarily obscure the gist of the present invention, such detailed description will be omitted.

[0042] Furthermore, the terms used in this application are used solely to describe specific embodiments and are not intended to limit the invention. Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as those generally understood by a person of ordinary skill in the art to which the invention pertains. Terms as defined in commonly used dictionaries should be interpreted as having the meaning consistent with their meaning in the context of the relevant art, and not as ideal or overly formal unless expressly defined in this application.

[0043] In this application, singular expressions include plural expressions unless they have a clearly different meaning in context.

[0044] In this application, various components may be used to describe them, but such components are not limited to those defined by the terms. The terms are used solely for the purpose of distinguishing one component from another.

[0045] In this application, terms such as "includes," "contains," or "has" refer to the existence of features, components (or constituent elements) described in the specification, and do not mean that one or more other features or components do not exist or cannot be added.

[0046] The present invention will be described in detail below.

[0047] The method for producing molybdenum dioxydichloride (MoO2Cl2) according to the present invention can be expressed as shown in chemical formula 5 below.

[0048] MoO3+SOCl2→MoO2Cl2+SO2 (chemical formula 5)

[0049] Specifically, the method for producing molybdenum dioxydichloride (MoO2Cl2) according to the present invention is: (i) The step of mixing anhydrous molybdenum trioxide and thionyl chloride in a solvent under inert gas conditions to produce a mixture ("first step of mixture production"); (ii) The step of raising the temperature of the generated mixture under an inert gas and stirring under reflux to generate a precipitated solid product ("second step of solid product generation"); and (iii) A step of separating and purifying molybdenum dioxydichloride (MoO2Cl2) from the solid product generated ("third step of separation and purification of molybdenum dioxydichloride (MoO2Cl2)");

[0050] Specifically, looking at each of the above stages, In the first step of producing the mixture, the ratio (moles) of molybdenum trioxide to thionyl chloride used may be less than 1:0.5 to 1:2.0, preferably 1:0.8 to 1:1.5, and more preferably 1:1.

[0051] The solvent in the first step of the mixture formation must be a non-coordinating solvent that does not react with or coordinate with the product molybdenum dioxydichloride (MoO2Cl2).

[0052] Specifically, the non-coordinating solvent may be an aliphatic or aromatic solvent containing a halogen element and having two or more carbon atoms.

[0053] The solvent may have a boiling point of 50°C to 200°C, preferably 70°C to 120°C, and most preferably 80°C to 100°C.

[0054] Specifically, the solvent may be one or more selected from the group consisting of tetrachloromethane (CCl4), 1,2-dichloroethane (C2H4Cl2), 1,1,1-trichloroethane, 1,1,2-trichloroethane (C2H3Cl3), and chlorobenzene (C6H5Cl).

[0055] The inert gas in the reaction vessel during the first stage of mixture formation and the second stage of solid product formation may be one or more gases selected from the group consisting of nitrogen (N2), argon (Ar), and helium (He).

[0056] In the second stage of solid product formation, the temperature rise for reflux stirring may be 50°C to 200°C, preferably 70°C to 120°C, and more preferably 80°C to 100°C. The reaction time for reflux stirring may be 16 hours to 72 hours.

[0057] In the third step of the separation and purification of the molybdenum dioxydichloride (MoO2Cl2), the separation is a step of filtering the resulting solid product, washing it with the solvent from the first step of the mixture formation, and drying it under vacuum to obtain molybdenum dioxydichloride (MoO2Cl2).

[0058] The purification is carried out by sublimating the dried molybdenum dioxydichloride (MoO2Cl2). [Modes for carrying out the invention]

[0059] The present invention will be described in more detail below based on the following examples.

[0060] <Example 1> 100 g (0.68 mol) of anhydrous molybdenum trioxide was added to a 1 L four-necked flask equipped with a magnetic stirring rod under inert gas. After adding 500 ml of anhydrous 1,2-dichloroethane, 82 g (0.68 mol) of thionyl chloride was gradually added at room temperature (MoO3:SOCl2 = 1:1 molar ratio).

[0061] The resulting mixture was stirred using a magnetic stirrer to create a white suspension. The suspension was then heated and refluxed under an inert gas atmosphere for 24 hours. During this time, a visible change in precipitate formation occurred.

[0062] The resulting yellowish-brown mixture was filtered to obtain a yellowish-brown solid product, which was washed with anhydrous 1,2-dichloroethane and then dried at room temperature using vacuum to obtain 127 g of molybdenum dioxydichloride (MoO2Cl2) (97% yield).

[0063] The obtained product (MoO2Cl2) was purified by sublimation (90°C / 180mtorr) to obtain 121 g of a pale yellow solid product (yield 87%).

[0064] The yellow solid product (MoO2Cl2) obtained was analyzed using TGA analysis, and the results of the TGA analysis were the same as those of molybdenum dioxydichloride (MoO2Cl2, CAS Number 13637-68-8) purchased from Sigma Aldrich. These results indicate that the compound produced by the method for producing molybdenum dioxydichloride of the present invention is molybdenum dioxydichloride (see Figure 1).

[0065] The aforementioned TGA analysis was performed using a Mettler Toledo TGA / DSC 3+, while the test sample was heated to 500°C at a rate of 10°C / min.

[0066] Furthermore, ICP-MS analysis showed that the obtained yellow solid product (MoO2Cl2) had a purity of 99.999% or higher (Figure 2).

[0067] The aforementioned ICP-MS analysis was performed using a Thermo Scientific XSeries 2.

[0068] <Example 2> Except for using 10 g (0.068 mol) of anhydrous molybdenum trioxide, 50 ml of anhydrous 1,2-dichloroethane, and 7.4 g (0.063 mol) of thionyl chloride (MoO3:SOCl2 = 1:0.9 molar ratio), the same method as in Example 1 was used to synthesize molybdenum dioxydichloride (MoO2Cl2) to obtain 12 g (yield 87%). The obtained molybdenum dioxydichloride (MoO2Cl2) was purified by sublimation in the same manner as in Example 1 to obtain 11 g (yield 79%) a pale yellow solid product (MoO2Cl2).

[0069] <Example 3> Except for using 10 g (0.068 mol) of anhydrous molybdenum trioxide, 50 ml of anhydrous 1,2-dichloroethane, and 9.9 g (0.083 mol) of thionyl chloride (MoO3:SOCl2 = 1:1.2 molar ratio), the synthesis was carried out in the same manner as in Example 1 to obtain 11 g of molybdenum dioxydichloride (MoO2Cl2) (yield 82%). The obtained molybdenum dioxydichloride (MoO2Cl2) was purified by sublimation in the same manner as in Example 1 to obtain 9 g of a pale yellow solid product (MoO2Cl2) (yield 69%).

[0070] <Example 4> The same method as in Example 1 was used for synthesis, and 10 g (0.068 mol) of anhydrous molybdenum trioxide, 50 ml of anhydrous 1,2-dichloroethane, and 8.2 g (0.069 mol) of thionyl chloride were used, and the mixture was stirred under reflux for 16 hours (MoO3:SOCl2 = 1:1). Before purification, 10 g of molybdenum dioxydichloride was obtained in 72% yield, and after purification, 9 g of a pale yellow solid product was obtained in 68% yield.

[0071] <Example 5> The same method as in Example 1 was used for synthesis, and 10 g (0.068 mol) of anhydrous molybdenum trioxide, 50 ml of anhydrous 1,2-dichloroethane, and 8.2 g (0.069 mol) of thionyl chloride were stirred at 60°C for 24 hours (MoO3:SOCl2 = 1:1). Before purification, 10 g of molybdenum dioxydichloride was obtained in 76% yield, and after purification, 7 g of a pale yellow solid product was obtained in 49% yield.

[0072] <Comparative Example 1> The same method as in Example 1 was used for synthesis, and the mixture was stirred under reflux for 24 hours using 10 g (0.068 mol) of anhydrous molybdenum trioxide, 50 ml of anhydrous heptane, and 8.2 g (0.069 mol) of thionyl chloride, but the desired molybdenum dioxydichloride could not be obtained.

[0073] <Comparative Example 2> The same method as in Example 1 was used for synthesis, and the mixture was stirred under reflux for 24 hours using 10 g (0.068 mol) of anhydrous molybdenum trioxide, 50 ml of anhydrous dichloromethane, and 8.2 g (0.069 mol) of thionyl chloride, but the desired molybdenum dioxydichloride could not be obtained.

[0074] <Comparative Example 3> The same method as in Example 1 was used for synthesis, and the mixture was stirred under reflux for 24 hours using 10 g (0.068 mol) of anhydrous molybdenum trioxide, 50 ml of anhydrous toluene, and 8.2 g (0.069 mol) of thionyl chloride, but the desired molybdenum dioxydichloride could not be obtained.

[0075] <Comparative Example 4> The same method as in Example 1 was used for synthesis, and a mixture of 10 g (0.068 mol) of anhydrous molybdenum trioxide, 50 ml of anhydrous 1,2-dichloroethane, and 16.4 g (0.136 mol) of thionyl chloride (MoO3:SOCl2 = 1:2 molar ratio) was stirred under reflux for 24 hours, but the desired molybdenum dioxydichloride could not be obtained.

[0076] While preferred embodiments of the present invention have been described above, the present invention is not limited to the specific embodiments described above, and it is of course possible for any person with ordinary skill in the art to carry out various modifications without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited to the embodiments described above, but should be defined not only by the claims described below, but also by equivalent claims, etc. [Industrial applicability]

[0077] As described above, the method for producing molybdenum dioxydichloride (MoO2Cl2) according to the present invention does not use chlorine gas or high reaction temperatures, making it safe and suitable for both small-scale and large-scale production, thus proving highly useful industrially.

Claims

1. A method for producing molybdenum dioxydichloride, (i) The step of mixing anhydrous molybdenum trioxide and thionyl chloride in a non-coordinating solvent under an inert gas to produce a mixture ("first step of mixture production"); (ii) The step of raising the temperature of the generated mixture under an inert gas and refluxing to generate a precipitated solid product ("second step of solid product generation"); and (iii) From the solid product produced above, molybdenum dioxydichloride (MoO ２ Cl ２ ) is separated and purified (molybdenum dioxydichloride (MoO ２ Cl ２ The third step of separation and purification of ) is included; The non-coordinating solvent is an aliphatic and aromatic solvent containing halogen elements and having two or more carbon atoms, having a boiling point of 50°C to 200°C. In the first step of producing the mixture, the ratio (moles) of molybdenum trioxide to thionyl chloride used is 1:0.8 to 1:1.5, characterized in that molybdenum dioxydichloride (MoO ２ Cl ２ A method for manufacturing )

2. The non-coordinating solvent is carbon tetrachloride (CCl ４ ), 1,2-dichloroethane (C ２ H ４ Cl ２ ), 1,1,1-trichloroethane, 1,1,2-trichloroethane (C ２ H ３ Cl ３ ), and chlorobenzene (C ６ H ５ Cl), and is one or more non-coordinating solvents selected from the group consisting of these, and the method for producing molybdenum dioxydichloride (MoO ２ Cl ２ ) according to claim 1.

3. In the first step of producing the mixture, the ratio (moles) of molybdenum trioxide to thionyl chloride used is 1:1, characterized in that the molybdenum dioxydichloride (MoO) according to claim 1 ２ Cl ２ A method for manufacturing )

4. The second step of generating the solid product, reflux stirring, is carried out at a temperature of 50°C to 200°C, characterized in that the molybdenum dioxydichloride (MoO) according to claim 1 ２ Cl ２ A method for manufacturing )

5. The inert gas in the reaction vessel during the first stage of mixture production and the second stage of solid product production is nitrogen (N ２ The molybdenum dioxydichloride (MoO) according to claim 1 is characterized by being one or more gases selected from the group consisting of ), argon (Ar), and helium (He). ２ Cl ２ A method for manufacturing )

6. The reaction time for reflux stirring is 16 to 72 hours, characterized in that the molybdenum dioxydichloride (MoO) according to claim 1. ２ Cl ２ A method for manufacturing )

7. Molybdenum dioxydichloride (MoO ２ Cl ２ The third step of the separation and purification of ) is characterized by a sublimation method, characterized in that the molybdenum dioxydichloride (MoO) according to claim 1 ２ Cl ２ A method for manufacturing )

Images