Preparation method of dichloromolybdenum dioxide
High-purity molybdenum dichloride was prepared by low-temperature reaction and depressurized sublimation, which solved the problems of high reaction temperature and high energy consumption in the existing technology, realized the preparation of high-purity molybdenum dichloride, and improved the thin film quality of chip manufacturing.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SUZHOU JINHONG GAS CO LTD
- Filing Date
- 2026-03-03
- Publication Date
- 2026-04-10
AI Technical Summary
In the existing technology, the synthesis method of molybdenum dichlorodioxide has high reaction temperature and high energy consumption, and the reaction conditions are difficult to control, resulting in insufficient film purity and narrow process window, which affects chip performance and reliability.
High-purity molybdenum dichloride was prepared by reacting molybdenum trioxide, carbon tetrachloride, and solvent under an inert atmosphere at 180℃-240℃ for 6-10 hours, followed by sublimation under reduced pressure.
The preparation of high-purity molybdenum dichlorodioxide at low temperature was achieved, with a purity >99% and molybdenum metal ion content >99.999%, solving the problems of insufficient purity and unstable process in the existing technology.
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Figure CN121823655A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of molybdenum dichloride dioxide preparation, and particularly relates to a preparation method of molybdenum dichloride dioxide. BACKGROUND
[0002] At present, the global semiconductor industry is accelerating the evolution towards smaller process nodes (such as 3nm, 2nm) and three-dimensional architectures (such as GAA transistors, 3D NAND). Traditional physical vapor deposition (PVD) technology has encountered technical bottlenecks such as uneven film coverage and poor step coverage when facing microstructures with extremely high aspect ratios, which seriously restricts the improvement of chip performance and yield. Atomic layer deposition (ALD) and chemical vapor deposition (CVD) technologies have become the core processes for preparing key thin film layers of the next generation of chips due to their excellent conformality, uniformity and precise film thickness control capabilities.
[0003] As an ideal molybdenum metal precursor, molybdenum dichloride dioxide (MoO2Cl2) can efficiently react with reducing agents such as hydrogen at low temperatures through ALD / CVD processes to deposit low-resistivity, high-purity, dense and pore-free molybdenum films. Molybdenum (Mo) is an ideal candidate to replace traditional copper / tungsten interconnection barrier layers and gate materials due to its low resistivity, excellent thermal stability and resistance to electromigration. Therefore, stable supply of high-purity molybdenum-based precursors is a key material cornerstone for promoting the manufacturing technology breakthroughs of advanced logic chips and high-end memory chips (such as 128 layers or more 3D NAND) in China and moving towards high-end industries.
[0004] In existing technologies, solid-state molybdenum precursors (such as MoCl3) generally have unstable mass flow, low vapor pressure and are prone to condensation in delivery pipelines and reaction chambers to form particulate contaminants, which leads to a series of problems such as insufficient film purity, narrow process window, high defect rate, and directly affects the performance and reliability of chips.
[0005] In contrast, MoO2Cl2 can achieve stable sublimation characteristics and high purity, providing predictable and repeatable mass flow. Mo precursors exhibit weak adsorption characteristics on the surface during deposition, which not only facilitates process cleaning but also makes it possible to achieve high-difficulty selective deposition, which is a leading technology direction for the manufacture of 3D structure chips in the future. Therefore, developing molybdenum precursor MoO2Cl2 with superior performance is an inherent driving force and inevitable choice for the progress of semiconductor process technology.
[0006] The conventional method for synthesizing MoO2Cl2 involves mixing molybdenum trioxide (MoO3) with activated carbon (C) in a certain proportion, and then reacting this mixture with chlorine gas at high temperatures (300℃-400℃) to generate the target product MoO2Cl2. The reaction equation is 2MoO3 + C + 2Cl2 → 2MoO2Cl2 + CO2. This method involves high reaction temperatures, high energy consumption, and difficult-to-control reaction conditions. Summary of the Invention
[0007] The purpose of this invention is to provide a method for preparing molybdenum dichlorodioxide, which has a low reaction temperature, low energy consumption, and easily controllable reaction conditions.
[0008] To achieve the above objectives, a specific embodiment of the present invention provides the following technical solution:
[0009] A method for preparing molybdenum dichlorodioxide, the method comprising the following steps:
[0010] Mix molybdenum trioxide, carbon tetrachloride, and a solvent;
[0011] Under an inert atmosphere, the temperature is raised to 180℃-240℃ to carry out the reaction, yielding molybdenum dioxide dichloride.
[0012] In one or more embodiments of the present invention, the molar ratio of molybdenum trioxide to carbon tetrachloride is 1:(0.9-1.1).
[0013] In one or more embodiments of the present invention, the solvent is toluene.
[0014] In one or more embodiments of the present invention, the mass ratio of molybdenum trioxide to solvent is 1:2 to 1:4.
[0015] In one or more embodiments of the present invention, the reaction temperature is 200°C.
[0016] In one or more embodiments of the present invention, the reaction time is 6h-10h.
[0017] In one or more embodiments of the present invention, after the reaction is completed, the mixture is cooled to room temperature, then the gas generated by the reaction is released, and then the temperature is raised to 110°C-115°C to evaporate the solvent.
[0018] In one or more embodiments of the present invention, the inert atmosphere is a nitrogen atmosphere.
[0019] In one or more embodiments of the present invention, the obtained molybdenum dichlorodioxide is subjected to depressurization sublimation under an inert atmosphere at a pressure of 1500 Pa to 1550 Pa, a temperature of 85°C to 100°C, and a time of 3 to 5 hours.
[0020] In one or more embodiments of the present invention, the purity of the molybdenum dichloride is >99%, and the molybdenum metal ion content is >99.9999%.
[0021] Compared with the prior art, the preparation method of the present invention has a low reaction temperature, easy control of reaction conditions, high reaction selectivity, and high purity of the target product molybdenum dichlorodioxide, with a purity of >99% and a molybdenum metal ion content of >99.9999%. Attached Figure Description
[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0023] Figure 1 This is a flowchart of a method for preparing molybdenum dichlorodioxide in one embodiment of the present invention. Detailed Implementation
[0024] To enable those skilled in the art to better understand the technical solutions in this disclosure, the technical solutions in the embodiments of this disclosure are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments in this disclosure, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this disclosure.
[0025] A specific embodiment of the present invention provides a method for preparing molybdenum dichlorodioxide, such as... Figure 1 As shown, the specific steps include:
[0026] Step 1: Mix molybdenum trioxide, carbon tetrachloride and solvent.
[0027] Specifically, the molar ratio of molybdenum trioxide (MoO3) to carbon tetrachloride (CCl4) is 1:(0.9-1.1), and the mass ratio of molybdenum trioxide to solvent is 1:2-1:4. Toluene is used as the solvent to improve reaction selectivity, ensuring that molybdenum trioxide reacts with carbon tetrachloride to form molybdenum dichlorodioxide, reducing the formation of other byproducts such as molybdenum pentachloride (MoCl5) or other molybdenum chloride oxides, and guaranteeing product purity.
[0028] In addition, by precisely controlling the molar ratio of molybdenum trioxide and carbon tetrachloride, the two can react to produce molybdenum dichloride.
[0029] Step 2: Under an inert atmosphere, the temperature is raised to 180℃-240℃ to carry out the reaction.
[0030] Specifically, molybdenum trioxide, carbon tetrachloride, and solvent are added to the reactor, the reactor is sealed, and the reactor is purged with nitrogen 10 times. The reactor is then heated in an oil bath to 180℃-240℃ and maintained for 6-10 hours.
[0031] In this step, the reaction formula is: 2MoO3 + 2CCl4 = 2MoO2Cl2 + 2COCl2.
[0032] Step 3: After the reaction is complete, allow the reactor to cool naturally to room temperature, then slowly open the gas phase valve of the reactor to release the gas generated by the reaction.
[0033] Step 4: After releasing the gas, reheat the reactor to 110℃-115℃ to evaporate the toluene solvent and obtain molybdenum dioxide dichloride.
[0034] Specifically, the purity of the product is improved by evaporating the toluene solvent.
[0035] Step 5: Sublime dichlorodioxide is obtained under reduced pressure in an inert atmosphere at a pressure of 1500 Pa-1550 Pa, a temperature of 85 ℃-100 ℃, and a time of 3 h-5 h.
[0036] Specifically, by reducing pressure and sublimating to improve the purity of the product, the molybdenum dioxide dichloride prepared by this invention has a purity of >99% and a molybdenum metal ion content of >99.9999%, exhibiting high purity.
[0037] The present invention will be further described in detail below with reference to specific embodiments.
[0038] Example 1
[0039] The preparation method of molybdenum dioxide dichloride in this embodiment is as follows:
[0040] Add 10.00g of molybdenum trioxide, 10.69g of carbon tetrachloride (dehydrated) and 30.00g of toluene (dehydrated) to the reactor, seal the reactor, and purge the reactor with nitrogen 10 times.
[0041] The reactor was heated to 180°C in an oil bath and maintained for 8 hours.
[0042] After the reaction was complete, the reactor was allowed to cool naturally to room temperature. The gas phase valve was then slowly opened to release the gas generated in the reaction. The reactor was then reheated to 110°C to evaporate the toluene solvent, yielding molybdenum dioxide dichloride.
[0043] The obtained molybdenum dichloride was subjected to depressurized sublimation under an argon atmosphere at a pressure of 1500 Pa and a temperature of 90 °C for 3 hours to obtain high-purity molybdenum dichloride.
[0044] Example 2
[0045] The preparation method of molybdenum dioxide dichloride in this embodiment is as follows:
[0046] Add 10.00g of molybdenum trioxide, 10.69g of carbon tetrachloride (dehydrated) and 30.00g of toluene (dehydrated) to the reactor, seal the reactor, and purge the reactor with nitrogen 10 times.
[0047] The reactor was heated to 200°C in an oil bath and maintained for 8 hours.
[0048] After the reaction was complete, the reactor was allowed to cool naturally to room temperature. The gas phase valve was then slowly opened to release the gas generated in the reaction. The reactor was then reheated to 110°C to evaporate the toluene solvent, yielding molybdenum dioxide dichloride.
[0049] The obtained molybdenum dichloride was subjected to depressurized sublimation under an argon atmosphere at a pressure of 1500 Pa and a temperature of 90 °C for 3 hours to obtain high-purity molybdenum dichloride.
[0050] Example 3
[0051] The preparation method of molybdenum dioxide dichloride in this embodiment is as follows:
[0052] Add 10.00g of molybdenum trioxide, 10.69g of carbon tetrachloride (dehydrated) and 30.00g of toluene (dehydrated) to the reactor, seal the reactor, and purge the reactor with nitrogen 10 times.
[0053] The reactor was heated to 220°C in an oil bath and maintained for 8 hours.
[0054] After the reaction was complete, the reactor was allowed to cool naturally to room temperature. The gas phase valve was then slowly opened to release the gas generated in the reaction. The reactor was then reheated to 110°C to evaporate the toluene solvent, yielding molybdenum dioxide dichloride.
[0055] The obtained molybdenum dichloride was subjected to depressurized sublimation under an argon atmosphere at a pressure of 1500 Pa and a temperature of 90 °C for 3 hours to obtain high-purity molybdenum dichloride.
[0056] Example 4
[0057] The preparation method of molybdenum dioxide dichloride in this embodiment is as follows:
[0058] Add 10.00g of molybdenum trioxide, 10.69g of carbon tetrachloride (dehydrated) and 30.00g of toluene (dehydrated) to the reactor, seal the reactor, and purge the reactor with nitrogen 10 times.
[0059] The reactor was heated to 240°C in an oil bath and maintained for 8 hours.
[0060] After the reaction was complete, the reactor was allowed to cool naturally to room temperature. The gas phase valve was then slowly opened to release the gas generated in the reaction. The reactor was then reheated to 110°C to evaporate the toluene solvent, yielding molybdenum dioxide dichloride.
[0061] The obtained molybdenum dichloride was subjected to depressurized sublimation under an argon atmosphere at a pressure of 1500 Pa and a temperature of 90 °C for 3 hours to obtain high-purity molybdenum dichloride.
[0062] Example 5
[0063] The preparation method of molybdenum dioxide dichloride in this embodiment is as follows:
[0064] Add 10.00g of molybdenum trioxide, 11.75g of carbon tetrachloride (dehydrated) and 30.00g of toluene (dehydrated) to the reactor, seal the reactor, and purge the reactor with nitrogen 10 times.
[0065] The reactor was heated to 200°C in an oil bath and maintained for 8 hours.
[0066] After the reaction was complete, the reactor was allowed to cool naturally to room temperature. The gas phase valve was then slowly opened to release the gas generated in the reaction. The reactor was then reheated to 110°C to evaporate the toluene solvent, yielding molybdenum dioxide dichloride.
[0067] The obtained molybdenum dichloride was subjected to depressurized sublimation under an argon atmosphere at a pressure of 1500 Pa and a temperature of 90 °C for 3 hours to obtain high-purity molybdenum dichloride.
[0068] Example 6
[0069] The preparation method of molybdenum dioxide dichloride in this embodiment is as follows:
[0070] Add 10.00g of molybdenum trioxide, 9.62g of carbon tetrachloride (dehydrated) and 30.00g of toluene (dehydrated) to the reactor, seal the reactor, and purge the reactor with nitrogen 10 times.
[0071] The reactor was heated to 200°C in an oil bath and maintained for 8 hours.
[0072] After the reaction was complete, the reactor was allowed to cool naturally to room temperature. The gas phase valve was then slowly opened to release the gas generated in the reaction. The reactor was then reheated to 110°C to evaporate the toluene solvent, yielding molybdenum dioxide dichloride.
[0073] The obtained molybdenum dichloride was subjected to depressurized sublimation under an argon atmosphere at a pressure of 1500 Pa and a temperature of 90 °C for 3 hours to obtain high-purity molybdenum dichloride.
[0074] The mass, yield, raw material amount and reaction conditions of molybdenum dichlorodioxide obtained in Examples 1-6 are shown in Table 1.
[0075] Table 1. Mass, yield, feedstock amounts, and reaction conditions of molybdenum dichlorodioxide obtained in each example.
[0076]
[0077] Comparative Example 1
[0078] The preparation method of molybdenum dioxide dichlorodioxide in this comparative example is as follows:
[0079] Add 10.00g of molybdenum trioxide, 10.69g of carbon tetrachloride (water-free) and 30.00g of N,N-dimethylformamide (DMF) to the reactor, seal the reactor, and purge the reactor with nitrogen 10 times.
[0080] The reactor was heated to 180°C in an oil bath and maintained for 8 hours.
[0081] After the reaction was complete, the reactor was allowed to cool naturally to room temperature. The gas phase valve was then slowly opened to release the gas generated in the reaction. The reactor was then reheated to 110°C to evaporate the N,N-dimethylformamide solvent, yielding molybdenum dioxide dichlorodioxide.
[0082] The obtained molybdenum dioxide dichloride was subjected to depressurized sublimation under an argon atmosphere, maintaining a pressure of 1500 Pa and a temperature of 90 °C for 3 hours.
[0083] Testing revealed that the purity of molybdenum dioxide dichloride obtained in this comparative example was significantly reduced, with the purity of the main component MoO2Cl2 being <99%, the purity of molybdenum metal ions being <99%, and the yield being <60%.
[0084] Comparative Example 2
[0085] The preparation method of molybdenum dioxide dichlorodioxide in this comparative example is as follows:
[0086] Add 10.00g of molybdenum trioxide, 8.55g of carbon tetrachloride (dehydrated) and 30.00g of toluene (dehydrated) to the reactor, seal the reactor, and purge the reactor with nitrogen 10 times.
[0087] The reactor was heated to 180°C in an oil bath and maintained for 8 hours.
[0088] After the reaction was complete, the reactor was allowed to cool naturally to room temperature. The gas phase valve was then slowly opened to release the gas generated in the reaction. The reactor was then reheated to 110°C to evaporate the toluene solvent, yielding molybdenum dioxide dichloride.
[0089] The obtained molybdenum dioxide dichloride was subjected to depressurized sublimation under an argon atmosphere, maintaining a pressure of 1500 Pa and a temperature of 90 °C for 3 hours.
[0090] Testing revealed that the purity of molybdenum dioxide dichloride obtained in this comparative example was significantly reduced, with the purity of the main component MoO2Cl2 being <99% and the purity of molybdenum metal ions being <99%.
[0091] As can be seen from Comparative Example 1 and the Examples, the present invention selects toluene as a solvent, which can effectively ensure the reaction selectivity of molybdenum trioxide and carbon tetrachloride, enabling the two to react to generate molybdenum dichlorodioxide, and reducing the generation of impurities, thus ensuring the purity of the product.
[0092] As can be seen from Comparative Example 2 and the Examples, the ratio between molybdenum trioxide and carbon tetrachloride affects the formation of the target product molybdenum dichlorodioxide. Within the ratio range disclosed in this invention, molybdenum trioxide and carbon tetrachloride can accurately react to form molybdenum dichlorodioxide, inhibiting the formation of other byproducts.
[0093] In Examples 1-6, under the reaction conditions and raw material amounts disclosed in this invention, molybdenum trioxide and carbon tetrachloride can generate molybdenum dichlorodioxide, exhibiting high yield and high purity. Among them, the reaction is optimal when the raw material ratio is 1:1 and the reaction temperature is 200°C, and the yield of molybdenum dichlorodioxide obtained is the highest.
[0094] It will be apparent to those skilled in the art that this disclosure is not limited to the details of the exemplary embodiments described above, and that this disclosure can be implemented in other specific forms without departing from the spirit or essential characteristics of this disclosure. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of this disclosure is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within this disclosure.
[0095] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A method for preparing molybdenum dioxide dichloride, characterized in that, The preparation method includes the following steps: Mix molybdenum trioxide, carbon tetrachloride, and a solvent; Under an inert atmosphere, the temperature is raised to 180℃-240℃ to carry out the reaction, yielding molybdenum dioxide dichloride.
2. The method for preparing molybdenum dichlorodioxide according to claim 1, characterized in that, The molar ratio of molybdenum trioxide to carbon tetrachloride is 1:(0.9-1.1).
3. The method for preparing molybdenum dichlorodioxide according to claim 1, characterized in that, The solvent is toluene.
4. The method for preparing molybdenum dichlorodioxide according to claim 3, characterized in that, The mass ratio of molybdenum trioxide to solvent is 1:2 to 1:
4.
5. The method for preparing molybdenum dichlorodioxide according to claim 1, characterized in that, The reaction temperature is 200℃.
6. The method for preparing molybdenum dichlorodioxide according to claim 1, characterized in that, The reaction time is 6-10 hours.
7. The method for preparing molybdenum dichlorodioxide according to claim 1, characterized in that, After the reaction is complete, the mixture is cooled to room temperature, the gas generated in the reaction is released, and then the temperature is raised to 110℃-115℃ to evaporate the solvent.
8. The method for preparing molybdenum dichlorodioxide according to claim 1, characterized in that, The inert atmosphere is a nitrogen atmosphere.
9. The method for preparing molybdenum dioxide dichloride according to claim 1, characterized in that, The obtained molybdenum dioxide dichloride was subjected to depressurization sublimation under an inert atmosphere at a pressure of 1500 Pa-1550 Pa, a temperature of 85 °C-100 °C, and a time of 3-5 h.
10. The method for preparing molybdenum dioxide dichlorodioxide according to claim 9, characterized in that, The purity of the molybdenum dioxide dichloride is >99%, and the molybdenum metal ion content is >99.9999%.