Continuous synthesis method of cobalt-based alkyne precursor based on micro-reaction reinforcement
By using microreaction enhancement technology to control the synthesis of cobalt-based alkyne precursors in a stacked microreactor array, the problems of uncontrollable reactions, poor selectivity, and safety hazards in traditional synthesis processes have been solved. This has enabled the preparation of high-purity cobalt-based alkyne complexes, meeting the material requirements of semiconductor devices.
Patent Information
- Application Number
- CN202511033341.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-25
- Publication Date
- 2025-11-18
AI Technical Summary
Existing cobalt-based alkyne precursor synthesis processes suffer from problems such as uncontrollable reactions, poor selectivity, safety hazards, high solvent consumption, low productivity, insufficient by-product generation, and low production efficiency.
Employing the field of microreaction enhancement, a reaction was carried out by passing a hexane solution of Co2(CO)8 with 3,3-dimethyl-1-butyne under nitrogen protection through a stacked microreactor array. The reaction process was controlled by inverted triangular staggered baffles and gradient temperature. The product composition was monitored by mass spectrometry and Fourier transform infrared spectroscopy, and high-purity mononuclear cobalt carbonyl alkyne complexes were collected.
The preparation of high-purity mononuclear cobalt carbonyl alkyne complexes was achieved, which improved the safety and selectivity of the reaction, reduced the purification difficulty, increased the yield, and met the material requirements of semiconductor devices.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of advanced electronic material preparation technology, in particular to a continuous synthesis method of cobalt-based alkyne precursor based on micro-reaction intensification. BACKGROUND
[0002] The cobalt-based alkyne precursor can be used for chemical vapor deposition (CVD) of cobalt interconnection material in semiconductor devices and atomic layer deposition (ALD) process of high-precision cobalt thin film in semiconductor. However, the existing synthesis process faces technical bottlenecks, including: (1) uncontrollable reaction: when the cobalt alkyne complex is synthesized by traditional liquid phase method, the substitution reaction of Co2(CO)8 and alkyne is easy to proceed excessively, which leads to complete dissociation of CO ligand in the product, generating unstable Co(0) species, which cannot meet the requirements of precursor reactivity for thin film deposition. (2) poor selectivity: the proportion of by-products (such as polynuclear cobalt cluster compounds) is as high as 20-30%, which needs multiple purification, and the yield is less than 60%. (3) safety hazard: Co2(CO)8 is sensitive to oxygen, and intermittent reaction is easy to cause local overheating and release of CO gas. (4) large solvent consumption: the solvent consumption of intermittent reaction kettle is large.
[0003] Therefore, it is an urgent problem for those skilled in the art to provide a continuous synthesis method of cobalt-based alkyne precursor which is safe in reaction, can improve reaction selectivity, avoid cluster generation, reduce purification difficulty and improve yield. SUMMARY
[0004] Therefore, the present application provides a continuous synthesis method of cobalt-based alkyne precursor based on micro-reaction intensification.
[0005] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:
[0006] A continuous synthesis method of cobalt-based alkyne precursor based on micro-reaction intensification, comprising the following steps:
[0007] (1) Pre-cool the Co2(CO)8 solution in n-hexane to-10℃ for standby;
[0008] (2) The Co2(CO)8 solution in n-hexane is introduced into the layered micro-reactor array under nitrogen protection to react, and after monitoring the product composition at the outlet of the layered micro-reactor array by mass spectrometry and Fourier infrared spectroscopy, the product is collected;
[0009] The layered micro-reactor array is composed of 3-6 micro-reactors in series; the micro-reactor is provided with at least one group of inverted triangular staggered baffles. When working, the inverted triangular staggered baffles are expanded under the impact of the material, and automatically closed when there is no material passing through.
[0010] Furthermore, the concentration of the hexane solution of Co2(CO)8 in step (1) is 0.05-0.12 mol / L.
[0011] Furthermore, in step (1), the mass ratio of Co2(CO)8 to 3,3-dimethyl-1-butyne is 1:1-1.5.
[0012] Furthermore, a temperature gradient is formed within the stacked microreactor array;
[0013] The inlet temperature of the stacked microreactor array is -10℃, and the outlet temperature is 40℃-60℃.
[0014] The throughput of the stacked microreactor array is 1.2 kg / h.
[0015] Furthermore, the microreactor has a diameter of 150 μm.
[0016] The beneficial effects of this invention are as follows: This invention prepares high-purity mononuclear cobalt carbonyl alkyne complexes via a controlled alkyne ligand substitution reaction in a continuous flow microchannel reactor. The compounds prepared by this invention can be used as key precursors in chemical vapor deposition (CVD) of cobalt interconnect materials in semiconductor devices and in atomic layer deposition (ALD) processes for high-precision cobalt thin films in semiconductors.
[0017] This invention utilizes a microchannel reaction system with a passivation layer to precisely control the substitution reaction process and combines it with in-situ detection technology to achieve the directed synthesis and collection of specific coordination structures. The resulting products exhibit excellent thermal stability and vapor pressure characteristics, meeting the requirements for precursor materials in advanced semiconductor device manufacturing. Attached Figure Description
[0018] Figure 1 This is a schematic diagram of the reaction process for preparing cobalt-based alkyne precursors based on microreaction enhancement according to the present invention;
[0019] Figure 2 The image shows the NMR spectrum of the product prepared in Example 1 of this invention. Detailed Implementation
[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0021] Example 1
[0022] (1) Equipment configuration: Microreactor: Stacked mixing channel made of 316L material (150μm in diameter). The inside of the microchannel is passivated by a dense Al2O3 coating to prevent pipeline corrosion.
[0023] (2) Pre-cool the hexane solution of Co2(CO)8 to -10℃ for later use;
[0024] (3) The hexane solution of Co2(CO)8 and 3,3-dimethyl-1-butyne were introduced into a stacked microreactor array under nitrogen protection. The product composition at the outlet of the stacked microreactor array was monitored by mass spectrometry and Fourier transform infrared spectroscopy, and the product was collected.
[0025] Table 1. Operational data for Example 1
[0026]
[0027] Example 2
[0028] The scheme is basically the same as that in Example 1, with the differences shown in Table 2.
[0029] Table 2. Operational data for Example 2
[0030]
[0031]
[0032] Example 3
[0033] The scheme is basically the same as that in Example 1, with the differences shown in Table 3.
[0034] Table 3. Operational data for Example 2
[0035]
[0036] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.
Claims
1. A continuous synthesis method for cobalt-based alkyne precursors based on microreaction enhancement, characterized in that, Includes the following steps: (1) Pre-cool the hexane solution of Co2(CO)8 to -10℃ for later use; (2) The hexane solution of Co2(CO)8 and 3,3-dimethyl-1-butyne were introduced into a stacked microreactor array under nitrogen protection. The product composition at the outlet of the stacked microreactor array was monitored by mass spectrometry and Fourier transform infrared spectroscopy, and the product was collected. The stacked microreactor array consists of 3-6 microreactors connected in series; each microreactor is equipped with at least one set of inverted triangular staggered baffles.
2. The continuous synthesis method for cobalt-based alkyne precursors based on microreaction enhancement according to claim 1, characterized in that, The concentration of the hexane solution of Co2(CO)8 mentioned in step (1) is 0.05-0.12 mol / L.
3. The continuous synthesis method for cobalt-based alkyne precursors based on microreaction enhancement according to claim 1, characterized in that, In step (1), the mass ratio of Co2(CO)8 to 3,3-dimethyl-1-butyne is 1:1-1.
5.
4. The continuous synthesis method for cobalt-based alkyne precursors based on microreaction enhancement according to claim 3, characterized in that, A temperature gradient is formed within the stacked microreactor array; The inlet temperature of the stacked microreactor array is -10℃, and the outlet temperature is 40℃-60℃.
5. The continuous synthesis method for cobalt-based alkyne precursors based on microreaction enhancement according to claim 4, characterized in that, The microreactor has a diameter of 150 μm.