CN112125931B - Synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI) - Google Patents
Synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI) Download PDFInfo
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- CN112125931B CN112125931B CN202011083752.0A CN202011083752A CN112125931B CN 112125931 B CN112125931 B CN 112125931B CN 202011083752 A CN202011083752 A CN 202011083752A CN 112125931 B CN112125931 B CN 112125931B
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- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
Abstract
The invention discloses a synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI), which relates to the technical field of new chemical material preparation and comprises the following steps: adding a solvent a, sodium tungstate, tert-butylamine and an acid binding agent into a reaction vessel, dropwise adding trimethylchlorosilane under ice water bath, controlling the temperature, and reacting after the dropwise adding is finished; filtering the reaction product, and distilling under reduced pressure to obtain a crude product of bis (tert-butylamine) tungsten dichloride; adding a crude product of bis (tertiary butylamine) tungsten dichloride into the solvent b, dropwise adding an n-hexane solution of lithium dimethylamino under an ice water bath, and stirring for reaction after the dropwise addition is finished; filtering the reaction product under the protection of argon, and distilling under reduced pressure to obtain the product. The invention provides a novel synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI), the raw materials required by the reaction are cheap and easy to obtain, the experimental operation is simple, the yield can reach 86.7%, the product purity is high, and the method has the operability of industrial production.
Description
Technical Field
The invention relates to the technical field of preparation of new chemical materials, in particular to a synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI).
Background
Copper is commonly used as a material for forming electronic circuits in semiconductor structures due to its good electrical conductivity, however, one disadvantage of copper is its high tendency to diffuse into SiO 2 Thereby severely affecting the performance of the integrated circuit. Therefore, to solve this problem, a barrier layer is required to prevent copper from diffusing into SiO 2.
Tungsten nitride (WN) is often used as a material for the barrier layer, and its thin film can be obtained by a magnetron co-sputtering method, but the uniformity inside the thin film is narrow enough to be suitable for microelectronic devices with narrow characteristics in the future. Atomic Layer Deposition (ALD) refers to a method of forming a thin film by alternately pulsing a vapor phase precursor into a reaction chamber and performing a vapor-solid phase chemisorption reaction on the surface of a deposition substrate, which produces a thin film coating having a highly uniform thickness, the uniformity of the thin film being derivable not only to flat substrate surfaces but also into trenches and holes having a narrow width. The ALD technique generally uses WF as a raw material for preparing the WN layer 6 And ammonia, the method can prepare a good WN coating, but HF gas generated by the reaction can erode SiO 2 Or Si substrate, and in addition, organic fluorine can remain on the surface of the WN layer in the process, so that the adhesion of the deposited WN coating on the copper surface is affected, and the performance of the whole material is affected.
Recent technology has shown that bis (t-butylamine) bis (dimethylamine) tungsten (VI) can be used in place of WF 6 The synthesis of bis (t-butylamine) bis (dimethylamine) tungsten (VI) becomes a very important task to produce a smoother, uniform barrier to WN, having the structural formula (i):
in the prior art, tungsten hexachloride and N-tertiary butyl trimethyl silicon-based amine are firstly used for synthesizing bis (tertiary butyl amine) tungsten dichloride, then the bis (tertiary butyl amine) tungsten dichloride and lithium dimethylamino at the temperature of minus 50 ℃ are used for dripping materials at a controlled temperature, and the room temperature is restored to react for 3 hours after the dripping materials are finished; after the reaction, lithium chloride is removed by filtration, the filtrate is concentrated to remove the solvent, and the concentrated residual liquid is distilled under reduced pressure to obtain colorless transparent liquid with the yield of 38% (KR 2020/41247,2020). The raw material N-tert-butyl trimethyl silicon-based amine required by the synthesis method is extremely expensive, the final yield is only 38%, the reaction requires ultralow temperature, and industrialization is difficult to realize.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI), the raw materials required by the reaction are cheap and easy to obtain, the process is simple, and the yield of the obtained product is high.
The invention provides a synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI), which comprises the following steps:
s1, adding a solvent a, sodium tungstate, tert-butylamine and an acid binding agent into a reaction vessel, dropwise adding trimethylchlorosilane under ice water bath, controlling the temperature, and carrying out reaction after dropwise adding;
s2, filtering and distilling the reaction product of the S1 under reduced pressure to obtain a crude product of bis (tertiary butylamine) tungsten dichloride;
s3, adding the crude product of bis (tertiary butylamine) tungsten dichloride into the solvent b, dropwise adding an n-hexane solution of lithium dimethylamino under ice water bath, and stirring for reaction after the dropwise addition is finished;
and S4, filtering the reaction product of the S3 under the protection of argon, and distilling under reduced pressure to obtain the catalyst.
Preferably, in S1, the solvent a is any of ethylene glycol dimethyl ether, tetrahydrofuran, methyl tetrahydrofuran, tert-butyl methyl ether.
Preferably, in S1, the acid binding agent is any of triethylamine, diethylamine, pyridine.
Preferably, in S1, trimethylchlorosilane is dropwise added in ice water bath, and the temperature is controlled to be 0-5 ℃.
Preferably, in S1, after the dropwise addition of trimethylchlorosilane is finished, the trimethylchlorosilane is reacted at 25-45 ℃ for 0.5-1 h, and then the mixture is refluxed and kept at the temperature for 10-12 h.
Preferably, in S3, the solvent b is any of toluene, n-hexane, n-heptane, cyclohexane.
Preferably, in S3, the n-hexane solution of the lithium dimethylamino is dropwise added under ice water bath, and the temperature is controlled to be between-10 and 30 ℃.
Preferably, in S3, stirring is carried out for 2-3 hours at 10-30 ℃ after the completion of the dripping.
Preferably, in S4, the reduced pressure distillation is to distill the solvent under reduced pressure at 20-30 ℃, then raise the temperature to 90 ℃ and distill the product under reduced pressure.
The beneficial effects are that: the invention provides a novel synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI), the raw materials required by the reaction are cheap and easy to obtain, the experimental operation is simple, the yield can reach 86.7%, the product purity is high, and the method has the operability of industrial production.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
400mL of ethylene glycol dimethyl ether, 40g of sodium tungstate, 69g of triethylamine, 21.9g of tert-butylamine and 177.3g of trimethylchlorosilane are added into a 1L three-neck round bottom flask in sequence, and the temperature is controlled to be 0-5 ℃. And (3) after the reaction is completed at the natural room temperature for 1h, and carrying out reflux heat preservation reaction for 12h. Filtering after heat preservation, decompressing and distilling to remove the solvent and the raw material to obtain 54g of crude tungsten dichloride of bis (tertiary butyl amine), adding the crude tungsten dichloride into 500ml of dry toluene solvent without purification, dropwise adding 410ml of 1mol/L of lithium dimethylamino-n-hexane solution in ice water bath, dropwise adding at the temperature of 5-10 ℃, and stirring for 3 hours at room temperature. Filtering under the protection of argon, distilling the filtrate at 20-30 ℃ under reduced pressure to remove the solvent, heating to 90 ℃ and distilling the product at reduced pressure to obtain 48.9g of orange-yellow transparent liquid, namely bis (tertiary butylamine) bis (dimethylamine) tungsten (VI), and obtaining 86.7 percent of yield;
elemental analysis: c (34.80%), N (13.51%), H (7.30%), W (44.40%)
Example 2
400mL of tetrahydrofuran, 40g of sodium tungstate, 69g of triethylamine, 21.9g of tert-butylamine and 177.3g of trimethylchlorosilane are added into a 1L three-neck round bottom flask in sequence, and the temperature is controlled to be 0-5 ℃. The reaction is completed at 35 ℃ for 45min, and the reflux heat preservation reaction is carried out for 11h. Filtering after heat preservation, decompressing and distilling to remove the solvent and the raw material to obtain 54g of crude tungsten dichloride of bis (tertiary-butylamine), adding the crude tungsten dichloride into 500ml of dry normal hexane solvent without purification, dropwise adding 410ml of 1mol/L of lithium dimethylamino normal hexane solution in ice water bath, dropwise adding at the temperature of 0 ℃, and stirring for 3h at the temperature of 10 ℃. Filtering under the protection of argon, distilling the filtrate at 20-30 ℃ under reduced pressure to remove the solvent, heating to 90 ℃ and distilling the product at reduced pressure to obtain 45.8g of orange-yellow transparent liquid, namely bis (tertiary butylamine) bis (dimethylamine) tungsten (VI), and obtaining the yield of 81.2%;
elemental analysis: c (34.83%), N (13.49%), H (7.25%), W (44.35%)
Example 3
400mL of ethylene glycol dimethyl ether, 40g of sodium tungstate, 69g of triethylamine, 21.9g of tert-butylamine and 177.3g of trimethylchlorosilane are added into a 1L three-neck round bottom flask in sequence, and the temperature is controlled to be 0-5 ℃. The mixture is reacted at 45 ℃ for 0.5h after dripping, and the reaction is carried out at reflux and heat preservation for 10h. Filtering after heat preservation, decompressing and distilling to remove the solvent and the raw material to obtain 54g of crude tungsten dichloride of bis (tertiary butyl amine), adding the crude tungsten dichloride into 500ml of dry toluene solvent without purification, dropwise adding 410ml of 1mol/L of lithium dimethylamino-n-hexane solution in ice water bath, dropwise adding at the temperature of 25-30 ℃, and stirring for 2h at the temperature of 30 ℃. Filtering under the protection of argon, distilling the filtrate at 20-30 ℃ under reduced pressure to remove the solvent, heating to 90 ℃ and distilling the product at reduced pressure to obtain 41.2g of orange-yellow transparent liquid, namely bis (tertiary butylamine) bis (dimethylamine) tungsten (VI), and obtaining 73% yield;
elemental analysis: c (34.81%), N (13.49%), H (7.29%), W (44.37%)
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. The synthesis method of bis (tertiary butylamine) bis (dimethylamine) tungsten (VI) is characterized by comprising the following steps:
s1, adding a solvent a, sodium tungstate, tert-butylamine and an acid binding agent into a reaction vessel, dropwise adding trimethylchlorosilane under ice water bath, controlling the temperature, and carrying out reaction after dropwise adding;
s2, filtering and distilling the reaction product of the S1 under reduced pressure to obtain a crude product of bis (tertiary butylamine) tungsten dichloride;
s3, adding the crude product of bis (tertiary butylamine) tungsten dichloride into the solvent b, dropwise adding an n-hexane solution of lithium dimethylamino under ice water bath, and stirring for reaction after the dropwise addition is finished;
s4, filtering the reaction product of the S3 under the protection of argon, and distilling under reduced pressure to obtain the catalyst;
s1, dropwise adding trimethylchlorosilane in ice water bath, and controlling the temperature to be 0-5 ℃;
in S1, after the dropwise addition of the trimethylchlorosilane is finished, the trimethylchlorosilane is reacted at 25-45 ℃ for 0.5-1 h, and then the trimethylchlorosilane is refluxed and kept at the temperature for 10-12 h.
2. The method for synthesizing bis (t-butylamine) bis (dimethylamine) tungsten (VI) according to claim 1, wherein in S1, the solvent a is any of ethylene glycol dimethyl ether, tetrahydrofuran, methyltetrahydrofuran, and t-butanol methyl ether.
3. The method for synthesizing bis (t-butylamine) bis (dimethylamine) tungsten (VI) according to claim 1, wherein the acid-binding agent in S1 is any of triethylamine, diethylamine, and pyridine.
4. The method for synthesizing bis (t-butylamine) bis (dimethylamine) tungsten (VI) according to claim 1, wherein in S3, the solvent b is any of toluene, n-hexane, n-heptane, and cyclohexane.
5. The method for synthesizing bis (t-butylamine) bis (dimethylamine) tungsten (VI) according to claim 1, wherein in S3, an n-hexane solution of lithium dimethylamino is added dropwise under ice water bath, and the temperature is controlled to be between-10 and 30 ℃.
6. The method for synthesizing bis (t-butylamine) bis (dimethylamine) tungsten (VI) according to claim 1, wherein in S3, the mixture is stirred at 10 to 30℃for 2 to 3 hours after completion of the dropwise addition.
7. The method for synthesizing bis (t-butylamine) bis (dimethylamine) tungsten (VI) according to claim 1, wherein in S4, the reduced pressure distillation is to distill the solvent at 20-30 ℃ under reduced pressure, then raise the temperature to 90 ℃ and distill the product under reduced pressure.
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| CN1675402A (en) * | 2002-07-12 | 2005-09-28 | 哈佛学院院长等 | Vapor deposition of tungsten nitride |
| CN103562434A (en) * | 2011-05-27 | 2014-02-05 | 株式会社艾迪科 | Method for manufacturing molybdenum oxide-containing thin film, starting material for forming molybdenum oxide-containing thin film, and molybdenum amide compound |
| TW201612354A (en) * | 2014-08-14 | 2016-04-01 | Air Liquide | Group 6 film forming compositions for vapor deposition of group 6 transition metal-containing films |
| CN112805290A (en) * | 2018-12-12 | 2021-05-14 | 优美科股份公司及两合公司 | Organometallic compounds |
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Patent Citations (4)
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| CN1675402A (en) * | 2002-07-12 | 2005-09-28 | 哈佛学院院长等 | Vapor deposition of tungsten nitride |
| CN103562434A (en) * | 2011-05-27 | 2014-02-05 | 株式会社艾迪科 | Method for manufacturing molybdenum oxide-containing thin film, starting material for forming molybdenum oxide-containing thin film, and molybdenum amide compound |
| TW201612354A (en) * | 2014-08-14 | 2016-04-01 | Air Liquide | Group 6 film forming compositions for vapor deposition of group 6 transition metal-containing films |
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