Preparation method and device of ethyl germane

Abstract

The invention relates to the field of special gas preparation, and mainly relates to a preparation method of ethyl germane, which comprises the following steps: generating GeH3 free radicals from germane under the action of electric field ionization, and then generating Ge2H6 through coupling of the GeH3 free radicals. According to the method, germane is changed into GeH3 free radicals, an e-free radical and an H free radical through ionization, then the free radicals are coupled to enable 2GeH3 to generate Ge2H6, and meanwhile, 2H free radicals generate H2, so that ethyl germane is obtained. In the preparation method disclosed by the invention, the conversion rate of the ethyl germane is high and is obviously improved compared with the conversion rate of the ethyl germane in the prior art, and the ethyl germane is generated by utilizing germane, so that the problem that a large amount of germane is generated along with generation of the ethyl germane is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of special gas preparation, in particular to a preparation method and device of germane. BACKGROUND

[0002] Germane compounds are key raw materials in the semiconductor industry, playing an important role in national development strategy. There are few existing synthesis processes for germane, and most of them are by-products of germane, such as patent CN 116924335 A discloses a method for preparing germane by reacting multi-metal germanium compound and ammonium chloride in liquid nitrogen medium, generating 45.6% germane and 31.9% germane. In the prior art, germane is also generated by hydrolysis of magnesium germanate and dilute acid, germane, and other higher germane. These reaction raw materials are not only scarce but also expensive, and the content of germane as a by-product is low, so whenever germane is generated, a large amount of germane will be produced. SUMMARY

[0003] The main purpose of the present application is to provide a preparation method and device of germane to solve the problem of generating a large amount of germane when generating germane in the prior art.

[0004] On the one hand, the present application provides a preparation method of germane, which comprises the steps of generating GeH3 radicals by ionizing germane under the action of an electric field, and then coupling the GeH3 radicals to generate Ge2H6. By ionizing germane into GeH3 radicals, one e - and one H radical, and then coupling the radicals to generate 2GeH3 into Ge2H6 and 2H radicals into H2, germane is obtained. In the preparation method of the present application, the conversion rate of germane is high, which is a significant improvement compared to the conversion rate of germane in the prior art, and germane is generated from germane, solving the problem of generating a large amount of germane for generating germane.

[0005] Preferably, the step of generating GeH3 radicals by ionizing germane under the action of an electric field, and then coupling the GeH3 radicals to generate Ge2H6 is completed under an inert gas protection atmosphere.

[0006] As the content of germane in the reaction increases, the temperature in the reaction device will rise, which will convert part of the germane into propyl germane, so inert gas is added to control the temperature and reduce the generation of by-products in the reaction. Nitrogen, helium, and argon can be selected as inert gases to reduce the reaction temperature.

[0007] Preferably, the step of generating GeH3 radicals from germane under the action of electric field ionization and then coupling the GeH3 radicals to generate Ge2H6 is completed under the condition of continuously supplying germane and inert gas into the reaction vessel, and when the volume flow rate of the supplied gas is 50-300 sccm, the volume fraction of the germane in the supplied gas is 0.5-20 %.

[0008] The reaction requires a large amount of inert gas to be supplied to absorb heat and reduce the reaction temperature, and when the volume flow rate of the gas is 50-300 sccm, the reaction of germane is relatively sufficient.

[0009] Preferably, the volume fraction of the germane is 1-2.5 %.

[0010] In this reaction, when the volume fraction of the germane participating in the reaction is in the range of 1-2.5 %, the conversion rate of germane is high, which is significantly higher than the conversion rate in the prior art.

[0011] Preferably, the electric field strength of the electric field providing the electric field ionization is 0.29-0.86 MV / m.

[0012] Under the action of the electric field, GeH4 will generate GeH3 radicals, one e - and H radicals, and then the coupling of the GeH3 radicals will generate germane and by-product higher germane.

[0013] Preferably, the preparation method comprises the following steps: S1, supplying inert gas into a reaction vessel having a discharge electrode, filling the reaction vessel with the inert gas, and electrifying the discharge electrode to make the reaction vessel have a continuous discharge electric field; S2, supplying a mixed gas of germane and inert gas into the reaction vessel, so that the germane generates GeH3 radicals under the electric field ionization reaction in the electric field formed in the step 1, and Ge2H6 is generated by coupling the GeH3 radicals.

[0014] The inert gas supplied adjusts the content of the germane and absorbs the heat of the reaction to reduce the temperature of the reaction and reduce the conversion rate of the by-products.

[0015] Preferably, the reaction vessel is connected with a valve for controlling pressure and opening and closing.

[0016] The valve is used to control the pressure in the reaction vessel and make the gas flow out.

[0017] Preferably, the volume flow rate of the mixed gas in the step 2 is 50-300 sccm, and the volume fraction of the germane is 0.5-20 %. Further comprising: S3, recovering the reaction product through a recovery pipeline connected with the pressure-reducing valve, purifying the reaction product, and obtaining germane.

[0018] The application also provides a device for preparing germane, which comprises a reaction container, a raw material input pipeline, a radio frequency power supply and a recovery pipeline. The reaction container is made of an insulating material, and an internal electrode and an external electrode are arranged on the inside and the outside of the reaction container respectively. One end of the raw material input pipeline is communicated with the reaction container, and the other end is communicated with a germane storage source and an inert gas storage source respectively. One end of the recovery pipeline is communicated with the reaction container, and the other end is communicated with a reaction product recovery container.

[0019] When the internal electrode is connected with the external electrode by the radio frequency power supply, the internal electrode is negative, the external electrode is positive, and a potential difference is generated between the internal electrode and the external electrode to provide an electric field required for ionizing germane into radicals.

[0020] The application provides a method for preparing germane by using germane, solves the problem that a large amount of germane is generated during the preparation of germane by other process methods, and improves the utilization rate of germane. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description.

[0022] The above merely describes the preferred embodiments of the application, and does not limit the patent scope of the application, and any equivalent structure transformation made according to the content of the application, or direct / indirect application in other related technical fields under the inventive concept of the application is included in the patent protection scope of the application.

[0023] Figure 1 It is a reaction device diagram of the application. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application. It should be noted that the embodiments and features in the embodiments can be combined with each other without conflict. Meanwhile, the raw materials mentioned below are not specifically described, and are all commercially available products. The method steps or preparation methods not specifically mentioned are all known to those skilled in the art.

[0025] The above description is only the preferred embodiments of the present application, and does not limit the patent scope of the present application. Any equivalent structural transformation based on the inventive concept of the present application, or direct / indirect application in other related technical fields is included in the patent protection scope of the present application.

[0026] The device and principle of the germane preparation method of the present application are as follows: The quartz tube with a length of 400 mm, an inner diameter of 15 mm and a wall thickness of 3 mm is selected as the reaction device, a thermometer is arranged on the quartz tube to test the temperature, the inert gas input pipe and the germane input pipe are connected to the inlet end of the quartz tube, the MFC control valve is arranged on the pipe to control the gas flow, the pressure control valve is arranged on the pipe to control the pressure, the output pipe is connected to the outlet of the quartz tube, and the pressure control valve is arranged on the output pipe. A 316 stainless steel rod with a diameter of 5 mm is inserted into the middle part of the pipe of the quartz tube as a negative electrode, a stainless steel mesh is wrapped on the outer surface of the quartz tube as a positive electrode, and an insulating material is covered on the surface of the positive electrode to prevent electric shock. The distance between the two electrodes is kept at 3.5 mm, so that the electric field distance is 3.5 mm, and the two electrodes are provided with an electric field by the radio frequency power supply.

[0027] The quartz tube is an insulating medium, a stainless steel rod is arranged inside as an inner electrode, and a stainless steel mesh is wrapped outside as an outer electrode. The radio frequency power supply is used to provide a voltage, so that an electric field is generated inside the quartz tube. The electrons in the electric field bombard GeH4, so that GeH3 radicals, an e - and H radicals are generated by electron transfer. Then, the GeH3 radicals are coupled to generate Ge2H6.

[0028] The operation steps of the preparation method are as follows: Leakage test: The vacuum and nitrogen replacement are carried out in the reaction system for multiple times to ensure that the vacuum degree of the system can reach 10 Pa.

[0029] Low-flow ignition: First, the inert gas, preferably helium, is flowed in at 30-50 sccm, so that the pressure rises to normal pressure. Then, the radio frequency power supply is turned on, and the voltage uniformity of the micro-discharge is observed.

[0030] Introducing germane: open the germane input pipe to introduce germane to the required content, and at the same time introduce helium, continuously maintain the volume flow rate of the introduced gas and maintain the pressure balance in the quartz tube, and at the same time control the power output of the radio frequency power supply to be stable.

[0031] Detecting gas: during the reaction, GC-TCD and PDD can be used to detect and calculate the volume fraction of GeH4, Ge2H6 and Ge3H8.

[0032] Parameter test: under the condition that the total flow rate is controlled at 200 sccm, the volume fraction of germane is gradually changed from 0.5% to 20% by adjusting the flow rate of introduced helium and the flow rate of germane, and the content of GeH4, Ge2H6 and Ge3H8 is tested after the introduction of gas. And for safety reasons, the whole reaction is kept at normal pressure.

[0033] GC-TCD or PDD is used for gas qualitative and quantitative analysis.

[0034] The electric field strength can be calculated by V / d.

[0035] Example 1 After the quartz tube is leak tested, helium is introduced into the quartz tube to reach the pressure of normal pressure. The output voltage of the radio frequency power supply is kept at 2 kV, under the condition that the total gas volume flow rate is 200 sccm, helium and germane accounting for 0.5% of the total introduced gas volume are continuously introduced, after the introduction of gas reaction, GC-TCD or PDD is used to detect and calculate the volume fraction of GeH4, Ge2H6 and Ge3H8, and a thermometer is used to test its temperature.

[0036] Example 2 After the quartz tube is leak tested, helium is introduced into the quartz tube to reach the pressure of normal pressure. The output voltage of the radio frequency power supply is kept at 2 kV, under the condition that the total gas volume flow rate is 200 sccm, helium and germane accounting for 1% of the total introduced gas volume are continuously introduced, after the introduction of gas reaction, GC-TCD or PDD is used to detect and calculate the volume fraction of GeH4, Ge2H6 and Ge3H8, and a thermometer is used to test its temperature.

[0037] Example 3 After the quartz tube is leak tested, helium is introduced into the quartz tube to reach the pressure of normal pressure. The output voltage of the radio frequency power supply is kept at 2 kV, under the condition that the total gas volume flow rate is 200 sccm, helium and germane accounting for 2.5% of the total introduced gas volume are continuously introduced, after the introduction of gas reaction, GC-TCD or PDD is used to detect and calculate the volume fraction of GeH4, Ge2H6 and Ge3H8, and a thermometer is used to test its temperature.

[0038] Example 4 After the leak test, helium was introduced into the quartz tube until the pressure reached the normal state. The output voltage of the radio frequency power supply was kept at 2 kV, and the total gas volume flow rate was 200 sccm. Helium and germane accounting for 5% of the total volume of the introduced gas were continuously introduced. After the reaction of the introduced gas, the volume fractions of GeH4, Ge2H6 and Ge3H8 were detected and calculated by using GC-TCD or PDD, and the temperature was tested by using a thermometer.

[0039] Example 5 After the leak test, helium was introduced into the quartz tube until the pressure reached the normal state. The output voltage of the radio frequency power supply was kept at 2 kV, and the total gas volume flow rate was 200 sccm. Helium and germane accounting for 10% of the total volume of the introduced gas were continuously introduced. After the reaction of the introduced gas, the volume fractions of GeH4, Ge2H6 and Ge3H8 were detected and calculated by using GC-TCD or PDD, and the temperature was tested by using a thermometer.

[0040] Example 6 After the leak test, helium was introduced into the quartz tube until the pressure reached the normal state. The output voltage of the radio frequency power supply was kept at 2 kV, and the total gas volume flow rate was 200 sccm. Helium and germane accounting for 20% of the total volume of the introduced gas were continuously introduced. After the reaction of the introduced gas, the volume fractions of GeH4, Ge2H6 and Ge3H8 were detected and calculated by using GC-TCD or PDD, and the temperature was tested by using a thermometer.

[0041] The content of each component in the quartz tube was tested by using GC-TCD or PDD. Under the reaction conditions of introducing different contents of GeH4, the test results of the peak area ratio of each component are shown in Table 1. The volume content of each component converted according to the test results in Table 1 and the temperature tested by the thermometer are shown in Table 2.

[0042] Table 1 Comparative Example 1 The difference between this comparative example and Example 2 is that inert gas was not introduced into the quartz tube, but pure germane was introduced. It was found that there was obvious germanium metal point attached to the wall of the quartz tube, which was judged to be germanium generation. The data of each component are shown in Table 2. The data in Table 2 represent the volume ratio of germane introduced to the total volume of introduced gas, the volume ratio of remaining germane to introduced germane, the volume ratio of generated digermane to introduced germane, and the volume ratio of generated trigermane to introduced germane.

[0043] Table 2 When the total volume flow rate of the input gas is 200 sccm, the more the input amount of germane is from 1% to 100%, the lower the conversion rate of germane is. The main reason is that the density of germane gradually increases with the increase of the input amount of germane, and the increase of the density leads to the increase of the reaction environment temperature, so that the environment is conducive to the conversion to by-product propyl germane, and the conversion rate of propyl germane is increased. When the input amount of germane is less than 1%, the conversion rate of germane is reduced, which may be because the coupling opportunity between GeH3 free radicals generated by ionization of germane is reduced due to the decrease of the input amount of germane, but the conversion rate of propyl germane is increased to a certain extent.

[0044] Example 7 The difference between the present example and Example 2 is that the potential generated by the radio frequency power source is different, and the volume ratio of generated germane to input germane under different potentials is shown in Table 3.

[0045] Table 3 From Example 7, we can see that when the potential generated by the radio frequency power source is 2kV, forming an electric field strength of 0.57M V / m, the conversion rate of germane is the highest, and with the increase of the electric field strength, the free radical concentration is large, the conversion rate of by-product propyl germane is gradually increased, and the conversion rate of germane is reduced. When the electric field strength is less than 0.57M V / m, the ionization efficiency of germane is low, and the content of ionized free radicals is small, so the conversion rate of germane is not high.

[0046] Example 8 The difference between the present example and Example 2 is that the total gas flow rate is different, and the volume ratio of generated germane to input germane under different gas flow rates is shown in Table 5.

[0047] Table 5 In Example 8, we can see that the slower the flow rate, the more sufficient the reaction is, and more germane is generated, and with the increase of the flow rate, the conversion rate of germane is gradually reduced. This is because the reaction time of germane in the quartz tube is increased with the decrease of the flow rate, and the reaction is sufficient, so the yield of germane is high. However, the absolute yield of germane produced is low when the flow rate is slow. Therefore, it is determined through experiments that when the total gas volume flow rate is 200 sccm, the yield of germane can be kept at a relatively high yield, and the absolute yield is also optimistic.

[0048] The above only describes the preferred embodiments of the present application, and does not limit the patent scope of the present application, and any equivalent structural transformation made according to the content of the present application, or direct / indirect application in other related technical fields is included in the patent protection scope of the present application.

Claims

1. A method for preparing diethylgermanane, characterized in that, The method includes the steps of generating GeH3 radicals by ionizing germane under an electric field, and then generating Ge2H6 by coupling the GeH3 radicals.

2. The method for preparing digerane according to claim 1, characterized in that, The step of generating GeH3 radicals by ionization under an electric field, and then generating Ge2H6 by coupling with the GeH3 radicals, is carried out under an inert gas protective atmosphere.

3. The method for preparing diethylgermanane as described in claim 1, characterized in that, The step of generating GeH3 free radicals by ionization under an electric field, and then generating Ge2H6 by coupling with the GeH3 free radicals, is carried out under the condition of continuously introducing germane and inert gas into the reaction vessel. When the volume flow rate of the introduced gas is 50~300 sccm, the volume fraction of germane in the introduced gas is 0.5~20%.

4. The method for preparing diethylgermanane as described in claim 3, characterized in that, The germane has a volume fraction of 1 to 2.5%.

5. The method for preparing diethylgermanane according to claim 1, characterized in that, The electric field strength providing the ionization effect is 0.29 M~0.86 MV / m.

6. The method for preparing digerane according to claim 2, characterized in that, Includes the following steps: S1. Inert gas is introduced into a reaction vessel with a discharge electrode to fill the reaction vessel with inert gas, and energize the discharge electrode to create a continuous discharge electric field in the reaction vessel. S2. A mixture of germane and inert gas is introduced into the reaction vessel, so that the germane is ionized in the electric field formed in step 1 to generate GeH3 free radicals, and Ge2H6 is generated through coupling of the GeH3 free radicals.

7. The method for preparing digerane according to claim 6, characterized in that, The reaction vessel is connected to valves that allow for pressure control and on / off switching.

8. The method for preparing digerane as described in claim 6 or 7, characterized in that, In step 2, the volumetric flow rate of the mixed gas is 50-300 sccm, and the volume fraction of the germane is 0.5-20%.

9. The method for preparing diethylgermanane as described in claim 8, characterized in that, Also includes: S3. The reaction product is recovered through a recovery pipeline connected to the pressure reducing valve, and the reaction product is purified to obtain diethylgermanium.

10. An apparatus for preparing diethylgermanane, used to implement the preparation method according to any one of claims 1 to 6, characterized in that, include: Reaction vessel, raw material input pipeline, radio frequency power supply, and recovery pipeline; The reaction vessel is made of a known insulating material, and its interior and outer surfaces are respectively provided with internal electrodes and external electrodes. The internal electrodes and the external electrodes are respectively connected to the negative and positive terminals of the radio frequency power supply, so that when powered by the radio frequency power supply, an electric field is generated in the reaction vessel that can ionize the germane and generate GeH3 free radicals. One end of the raw material input pipeline is connected to the reaction vessel, and the other end is connected to a germane storage source and an inert gas storage source, respectively. A valve that can independently control the flow rate of germane is provided between the germane storage source and the raw material input pipeline, and a valve that can independently control the flow rate of inert gas is provided between the inert gas storage source and the raw material input pipeline. One end of the recovery pipeline is connected to the reaction vessel, and the other end is connected to the reaction product recovery vessel. A pressure reducing valve is installed on the recovery pipeline to control the pressure inside the reaction vessel.

Images