Group III metal organic compounds for semiconductor industry and preparation method thereof

Abstract

The present invention discloses a Group III metal organic compound for use in the semiconductor industry and a preparation method thereof. The preparation method comprises reacting R2MCl with a Grignard reagent (CH3)2N-(CH2)3-MgCl to obtain R2M-(CH2)3-N(CH3)2; wherein R is CH3, C2H5, C3H7, or i-C3H7; and M is In, Ga, or Al. The synthesis preparation method of the present invention is simple to operate, low in cost, and can obtain an organometallic compound for use in the semiconductor industry with high organic and inorganic purities, such as preparing high-purity [3-(dimethylamino)propyl]dimethylindium, [3-(dimethylamino)propyl]dimethylgallium, [3-(dimethylamino)propyl]dimethylaluminum, [3-(dimethylamino)propyl]diethylgallium, and [3-(dimethylamino)propyl]dipropylindium, thereby meeting the semiconductor industry's requirements for high-purity finished products.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and in particular relates to a group III metal organic compound for use in the semiconductor industry and a preparation method thereof. Background Art

[0002] In the periodic table, a large number of Group III, IV, and V elements have been applied in the semiconductor industry. For example, the Group VA element phosphorus combines with indium to form narrow-bandgap semiconductor materials such as indium phosphide, which is used in the manufacture of optical communication devices. The Group VA element arsenic combines with gallium to form narrow-bandgap semiconductor materials such as gallium arsenide, which is used in the manufacture of high-frequency and optoelectronic devices. Gallium arsenide and indium phosphide used in optoelectronic devices can currently be grown using MOCVD (metal-organic chemical vapor deposition). The most common method involves reacting metal-organic compounds (MTCs) such as trimethylgallium (TMGa) and trimethylindium (TMIn) from Group IIIA sources with arsine (AsH3) and phosphine (PH3) from Group V sources to produce the desired products. However, other common metal-organic compounds, such as TMGa and TMIn, are highly reactive, flammable in air, and potentially explosive when exposed to water, posing a high safety risk.

[0003] Publication number CN116459540A provides a method for preparing [3-(dimethylamino)propyl]dimethylindium. This patent first dissolves indium using an electrolytic device, then adds iodomethane, acetonitrile, and ether using a specific device to produce dimethylindium iodide. The resulting dimethylindium iodide is then reacted with 3-(dimethylamino)propyllithium and distilled to obtain [3-(dimethylamino)propyl]dimethylindium. The [3-(dimethylamino)propyl]dimethylindium obtained by this reaction is in a liquid state at room temperature and does not significantly react with air and water, making it safer and having good purity and yield. However, this method requires the use of a specific synthesis device, which incurs a high synthesis cost.

[0004] Therefore, in view of the above technical problems, it is necessary to provide a method for preparing [3-(dimethylamino)propyl]dimethylindium or other metal organic compounds used in the semiconductor industry with simpler operation and lower synthesis cost.

[0005] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the Invention

[0006] The object of the present invention is to provide a group III metal organic compound for use in the semiconductor industry and a preparation method thereof, which has simple operation, low cost and high purity.

[0007] In order to achieve the above object, a specific embodiment of the present invention provides the following technical solutions:

[0008] A method for preparing a Group III metal organic compound for use in the semiconductor industry, comprising:

[0009] R2MCl reacts with Grignard reagent (CH3)2N-(CH2)3-MgCl to obtain R2M-(CH2)3-N(CH3)2;

[0010] wherein R is CH3, C2H5, C3H7 or i-C3H7;

[0011] M is In, Ga or Al.

[0012] In one or more embodiments of the present invention, the preparation method comprises the following steps:

[0013] Under an inert atmosphere, R3M reacts with MCl3 in a solvent to obtain R2MCl;

[0014] Magnesium chips and (CH3)2N-(CH2)3-Cl are prepared into Grignard reagent in a solvent;

[0015] R2MCl reacts with the above Grignard reagent and the solvent is removed to obtain a crude product of R2M-(CH2)3-N(CH3)2;

[0016] The crude product was subjected to vacuum distillation to obtain the pure product.

[0017] In one or more embodiments of the present invention, the molar ratio of R3M to MCl3 is 2:1.

[0018] In one or more embodiments of the present invention, the ratio of R2MCl to Grignard reagent is calculated as the molar ratio of MCl3 to (CH3)2N-(CH2)3-Cl, and the molar ratio of MCl3 to (CH3)2N-(CH2)3-Cl is 1:3-3.05.

[0019] In one or more embodiments of the present invention, when preparing R2MCl, the reaction temperature is 40-80°C and the reaction time is 3-6 hours; and / or, when preparing the Grignard reagent, the reaction temperature is 40-80°C and the reaction time is 2-4 hours; and / or, in the reaction of R2MCl and Grignard reagent, the reaction temperature is 40-80°C and the reaction time is 3-6 hours.

[0020] In one or more embodiments of the present invention, when preparing R2MCl, R3M and a solvent are mixed, and MCl3 and a solvent are mixed, and then reacted;

[0021] The mass ratio of R3M to solvent is 1:1.5-2.5;

[0022] The mass ratio of MCl3 to solvent is 1:1.5-2.5;

[0023] The solvent is one of n-hexane, diethyl ether and tetrahydrofuran.

[0024] In one or more embodiments of the present invention, after the reaction of R2MCl and Grignard reagent is completed, the solvent is distilled off, and the fraction with a top temperature of 55-100°C / 4 mmHg is collected by reduced pressure distillation to obtain a crude product.

[0025] In one or more embodiments of the present invention, during vacuum distillation, when R is CH3, if M is In, a fraction with a top temperature of 55-59°C / 4 mmHg is collected; if M is Ga, a fraction with a top temperature of 64-66°C / 7.5 mmHg is collected; if M is Al, a fraction with a top temperature of 59-61°C / 3 mmHg is collected;

[0026] And / or, during vacuum distillation, when R is C2H5, if M is In, collect the fraction with a top temperature of 77-81°C / 2.25 mmHg; if M is Ga, collect the fraction with a top temperature of 87-90°C / 7.5 mmHg; if M is Al, collect the fraction with a top temperature of 103-106°C / 7.5 mmHg;

[0027] And / or, during vacuum distillation, when R is C3H7, if M is In, collect the fraction with a top temperature of 60-63°C / 0.04 mmHg; if M is Ga, collect the fraction with a top temperature of 96-99°C / 0.008 mmHg;

[0028] And / or, during vacuum distillation, when R is i-C3H7, if M is In, collect the fraction with a top temperature of 52-55°C / 0.15 mmHg; if M is Ga, collect the fraction with a top temperature of 85-87°C / 0.008 mmHg.

[0029] In one or more embodiments of the present invention, the inert atmosphere is nitrogen.

[0030] In one or more embodiments of the present invention, the synthetic route is:

[0031] R2MCl+(CH3)2N-(CH2)3-MgCl→R2M-(CH2)3-N(CH3)2+MgCl2.

[0032] In one or more embodiments of the present invention, when preparing the Grignard reagent, the molar ratio of magnesium turnings to (CH3)2N-(CH2)3-Cl is 1.1-1.2:1;

[0033] And / or, when preparing the Grignard reagent, the mass ratio of the solvent to (CH3)2N-(CH2)3-Cl is 1.5-2.5:1.

[0034] Another specific embodiment of the present invention provides a technical solution as follows:

[0035] The group III metal organic compound used in the semiconductor industry is prepared by the above preparation method.

[0036] Compared with the patent with publication number CN116459540A, the preparation method of the present invention is simpler in operation, does not require a specific synthesis device, and can be completed in a glass flask. The raw material 3-(dimethylamino)propyl chloride is more easily available than 3-(dimethylamino)propyl lithium, is low in cost, and the obtained [3-(dimethylamino)propyl]dimethylindium has high purity, which can meet the purity requirements of the semiconductor industry. In addition, the preparation method of the present invention can also be used to prepare [3-(dimethylamino)propyl]dimethylgallium, [3-(dimethylamino)propyl]dimethylaluminum, [3-(dimethylamino)propyl]diethylgallium, and [3-(dimethylamino)propyl]dipropyl indium. High-purity products can also be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0038] Figure 1 For the product in Example 2 of the present invention 1 H NMR spectrum.

[0039] Figure 2 This is the ICP-OES diagram of the product in Example 2 of the present invention. DETAILED DESCRIPTION

[0040] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0041] Unless expressly stated otherwise, throughout the specification and claims, the term "comprise" or variations such as "include" or "comprising", etc., will be understood to include the stated elements or components but not to exclude other elements or other components.

[0042] Based on the synthesis cost and difficulty, the present invention selects 3-(dimethylamino)propyl chloride, which has a relatively wide source, to prepare a Grignard reagent. The Grignard reagent is used to undergo a substitution reaction with dimethylindium chloride to ultimately obtain [3-(dimethylamino)propyl]dimethylindium. The overall preparation method is simple, and the yield and purity are high.

[0043] In addition, based on this preparation concept, that is, the synthetic route R2MCl+(CH3)2N-(CH2)3-MgCl→R2M-(CH2)3-N(CH3)2+MgCl2, the present invention reacts the Grignard reagent with the metal halide to obtain [3-(dimethylamino)propyl]dimethylgallium, [3-(dimethylamino)propyl]dimethylaluminum, [3-(dimethylamino)propyl]diethylgallium and [3-(dimethylamino)propyl]dipropyl, which are similar in structure to [3-(dimethylamino)propyl]dimethylindium. Finally, high-purity products can be obtained through vacuum distillation. Taking [3-(dimethylamino)propyl]dimethylindium as an example, the specific synthetic process is as follows:

[0044] InCl3+2In(CH3)3→3In(CH3)2Cl;

[0045] (CH3)2N-(CH2)3-Cl+Mg→(CH3)2N-(CH2)3-MgCl;

[0046] In(CH3)2Cl+(CH3)2N-(CH2)3-MgCl→(CH3)2In-(CH2)3-N(CH3)2+MgCl2.

[0047] One embodiment of the present invention discloses a method for preparing a Group III metal organic compound for use in the semiconductor industry, comprising:

[0048] R2MCl reacts with Grignard reagent (CH3)2N-(CH2)3-MgCl to obtain R2M-(CH2)3-N(CH3)2;

[0049] wherein R is CH3, C2H5, C3H7 or i-C3H7;

[0050] M is In, Ga or Al.

[0051] In one embodiment, the method for preparing a Group III metal organic compound for use in the semiconductor industry comprises steps 1-4.

[0052] Step 1: Under an inert atmosphere, R3M and MCl3 are reacted in a solvent to obtain R2MCl.

[0053] Specifically, the inert atmosphere is nitrogen to prevent the reactants from reacting with oxygen. R3M and a solvent are mixed at a mass ratio of 1:1.5-2.5, and MCl3 and a solvent are mixed at a mass ratio of 1:1.5-2.5. The solvent is n-hexane, diethyl ether, or tetrahydrofuran. R3M and MCl3 are reacted in a solvent system at a molar ratio of 2:1 at a reaction temperature of 40-80°C for 3-6 hours. This reaction system ensures effective contact and sufficient reaction between the two, thereby improving product yield.

[0054] Step 2: Prepare a Grignard reagent by mixing magnesium chips and (CH3)2N-(CH2)3-Cl in a solvent.

[0055] Specifically, the solvent is one of n-hexane, diethyl ether, and tetrahydrofuran. The reaction is carried out at a molar ratio of magnesium chips to (CH3)2N-(CH2)3-Cl of 1.1-1.2:1 and a mass ratio of the solvent to (CH3)2N-(CH2)3-Cl of 1.5-2.5:1. The reaction temperature is 40-80°C and the reaction time is 2-4 hours. A slight excess of magnesium chips compared to (CH3)2N-(CH2)3-Cl facilitates the complete reaction of (CH3)2N-(CH2)3-Cl and improves the utilization rate of the reactants.

[0056] Step 3, R2MCl reacts with the above Grignard reagent to obtain crude R2M-(CH2)3-N(CH3)2.

[0057] Specifically, R2MCl and a Grignard reagent are reacted in a molar ratio of MCl3 to (CH3)2N-(CH2)3-Cl of 1:3-3.05, at a reaction temperature of 40-80°C for 3-6 hours. A slight excess of (CH3)2N-(CH2)3-Cl facilitates the formation of the target product. After the reaction, the crude product is first distilled to remove the solvent. When the solvent is n-hexane, the distillation temperature is 69-79°C; when the solvent is ether, the distillation temperature is 34-50°C; when the solvent is tetrahydrofuran, the distillation temperature is 66-76°C. Then, the crude product is obtained by vacuum distillation by collecting the fraction with a top temperature of 55-100°C / 4 mmHg. Pre-removal of the solvent prevents solvent contamination during fraction collection. Selecting a fraction within a certain temperature range can balance purity and yield.

[0058] Step 4: subjecting the crude product to vacuum distillation to obtain a pure product.

[0059] Specifically, when R is CH3, if M is In, collect the fraction with a top temperature of 55-59°C / 4 mmHg; if M is Ga, collect the fraction with a top temperature of 64-66°C / 7.5 mmHg; if M is Al, collect the fraction with a top temperature of 59-61°C / 3 mmHg; when R is C2H5, if M is In, collect the fraction with a top temperature of 77-81°C / 2.25 mmHg; if M is Ga, collect the fraction with a top temperature of 87-90°C / 7.5 mmHg; if M is Al , collecting the fraction with a top temperature of 103-106°C / 7.5mmHg; when R is C3H7 and M is In, collecting the fraction with a top temperature of 60-63°C / 0.04mmHg; if M is Ga, collecting the fraction with a top temperature of 96-99°C / 0.008mmHg; when R is i-C3H7 and M is In, collecting the fraction with a top temperature of 52-55°C / 0.15mmHg; if M is Ga, collecting the fraction with a top temperature of 85-87°C / 0.008mmHg. Choosing vacuum distillation is beneficial for obtaining a higher purity product and can reduce the occurrence of side reactions.

[0060] The present invention will be further described below with reference to specific embodiments.

[0061] Example 1

[0062] A method for preparing [3-(dimethylamino)propyl]dimethylindium comprises the following steps:

[0063] Under an anhydrous, oxygen-free nitrogen atmosphere, 121g of indium trichloride was mixed with a 363g indium trichloride n-hexane solution. Then, 175g of trimethylindium was mixed with a 525g trimethylindium n-hexane solution. The indium trichloride n-hexane solution was added to a 2L reactor, and the trimethylindium n-hexane solution was then added dropwise while stirring. The reactor temperature was maintained at 50°C. After the addition was complete, the reactor was heated to reflux and the reaction temperature was maintained at 50°C for 3 hours to obtain a dimethylindium chloride n-hexane solution.

[0064] Under a nitrogen atmosphere, add 43g of magnesium chips and 400g of n-hexane to another 2L reactor. Take 200g of anhydrous N,N-dimethyl-3-chloropropylamine and first add 15mL of N,N-dimethyl-3-chloropropylamine to the reactor. Stir while heating. Turn off the heat when the reaction is initiated, the solution becomes turbid, and the reaction reflux accelerates. Then, add the remaining N,N-dimethyl-3-chloropropylamine dropwise through a constant pressure funnel at a rate of 1 drop / s. The reactor temperature is controlled at 60°C during the addition. After the addition is complete, maintain the reactor temperature at 60°C and heat under reflux for 2h. After the end, the Grignard reagent is obtained and cooled to room temperature for later use.

[0065] The Grignard reagent was filtered and added dropwise to a solution of dimethylindium chloride in n-hexane. Stirring was performed dropwise, and the reaction temperature was maintained at 60°C. After the addition was completed, the reactor temperature was maintained at 50°C for 2 hours. After the reaction was completed, the n-hexane was distilled off at 69°C. After the system was cooled to room temperature, the fraction with a top temperature of 50-100°C / 4 mmHg was collected by vacuum distillation to obtain crude [3-(dimethylamino)propyl]dimethylindium.

[0066] The crude [3-(dimethylamino)propyl]dimethylindium was distilled through a vacuum distillation apparatus, the refrigerator temperature was set to 18±2°C, and the top temperature 55-59°C / 4mmHg fraction was collected to obtain 186g of pure [3-(dimethylamino)propyl]dimethylindium.

[0067] According to calculation, the yield of [3-(dimethylamino)propyl]dimethylindium in this embodiment is 48.3%, and the product is 1 The organic purity was 98.7% as determined by H NMR, and the inorganic purity reached 6N as determined by ICP-OES (inductively coupled plasma atomic emission spectrometry).

[0068] Example 2

[0069] A method for preparing [3-(dimethylamino)propyl]dimethylindium comprises the following steps:

[0070] Under an anhydrous, oxygen-free nitrogen atmosphere, 295g of indium trichloride was added to an ether solution of 885g of indium trichloride. Then, 427g of trimethylindium was added to an ether solution of 1281g of trimethylindium. The indium trichloride ether solution was added to a 5L reactor, and then the trimethylindium ether solution was added dropwise while stirring, maintaining the reactor temperature at 40°C. After the addition was completed, the reactor was heated to reflux, and the reaction temperature was maintained at 40°C for 5 hours to obtain a dimethylindium chloride ether solution.

[0071] Under a nitrogen atmosphere, add 106g of magnesium chips and 974g of ether to another 5L reactor. Take 487g of anhydrous N,N-dimethyl-3-chloropropylamine and first add 20mL of N,N-dimethyl-3-chloropropylamine to the reactor. Stir while heating. Turn off the heat when the reaction is initiated, the solution becomes turbid, and the reaction reflux accelerates. Then, add the remaining N,N-dimethyl-3-chloropropylamine dropwise through a constant pressure funnel at a rate of 1 drop / s. The reactor temperature is controlled at 40°C during the addition. After the addition is complete, maintain the reactor temperature at 40°C and heat under reflux for 4h. After the end, the Grignard reagent is obtained and cooled to room temperature for later use.

[0072] The Grignard reagent was filtered and added dropwise to a dimethylindium chloride ether solution with stirring while adding dropwise. The reaction temperature was maintained at 60°C. After the addition was completed, the reactor temperature was maintained at 40°C for 4 hours. After the reaction was completed, the ether was distilled off at 34°C. After the system was cooled to room temperature, the fraction with a top temperature of 50-100°C / 4 mmHg was collected by vacuum distillation to obtain crude [3-(dimethylamino)propyl]dimethylindium.

[0073] The crude [3-(dimethylamino)propyl]dimethylindium was distilled through a vacuum distillation apparatus with the refrigerator temperature set to 18±2°C. The top temperature fraction of 55-59°C / 4 mmHg was collected to obtain 436 g of pure [3-(dimethylamino)propyl]dimethylindium.

[0074] According to calculation, the yield of [3-(dimethylamino)propyl]dimethylindium in this embodiment is 47.2%, and the product is 1 H NMR analysis showed an organic purity of 99.1%. Figure 1 The corresponding H NMR spectrum is shown in Figure 2. The inorganic purity was determined to be 6N by ICP-OES (Inductively Coupled Plasma Atomic Emission Spectrometry).

[0075] Example 3

[0076] A method for preparing [3-(dimethylamino)propyl]dimethylindium comprises the following steps:

[0077] Under an anhydrous, oxygen-free nitrogen atmosphere, 307g of indium trichloride was added to a 921g tetrahydrofuran solution of indium trichloride. Then, 444g of trimethylindium was added to a 1332g tetrahydrofuran solution of trimethylindium. The tetrahydrofuran solution of indium trichloride was added to a 5L reactor, and then the tetrahydrofuran solution of trimethylindium was added dropwise while stirring, maintaining the reactor temperature at 60°C. After the addition was completed, the reactor was heated to reflux, and the reaction temperature was maintained at 60°C for 5 hours to obtain a tetrahydrofuran solution of dimethylindium chloride.

[0078] Under a nitrogen atmosphere, add 110g of magnesium chips and 1012g of tetrahydrofuran to another 5L reactor, take 506g of anhydrous N,N-dimethyl-3-chloropropylamine, add 20mL of N,N-dimethyl-3-chloropropylamine to the reactor, stir while heating, and turn off the heat when the reaction is initiated, the solution color becomes turbid, and the reaction reflux accelerates. Then, add the remaining N,N-dimethyl-3-chloropropylamine dropwise through a constant pressure funnel at a drop rate of 1s / drop, and control the reactor temperature at 70°C during the addition. After the addition is complete, maintain the reactor temperature at 70°C and heat under reflux for 4h. After the end, the Grignard reagent is obtained and cooled to room temperature for standby use.

[0079] The Grignard reagent was filtered and added dropwise to a tetrahydrofuran solution of dimethylindium chloride with stirring while adding dropwise. The reaction temperature was maintained at 60°C. After the addition was completed, the reactor temperature was maintained at 60°C for 4 hours. After the reaction was completed, tetrahydrofuran was distilled off at 66°C. After the system was cooled to room temperature, the fraction with a top temperature of 50-100°C / 4 mmHg was collected by vacuum distillation to obtain crude [3-(dimethylamino)propyl]dimethylindium.

[0080] The crude [3-(dimethylamino)propyl]dimethylindium was distilled through a distillation apparatus, the refrigerator temperature was set to 18±2°C, and the top temperature 55-59°C / 4mmHg fraction was collected to obtain 451g of pure [3-(dimethylamino)propyl]dimethylindium.

[0081] According to calculation, the yield of [3-(dimethylamino)propyl]dimethylindium in this embodiment is 46.9%, and the product is 1 The organic purity was 98.9% as determined by H NMR, and the inorganic purity was 6N as determined by ICP-OES (inductively coupled plasma atomic emission spectrometry).

[0082] Example 4

[0083] A method for preparing [3-(dimethylamino)propyl]dimethylindium comprises the following steps:

[0084] Under an anhydrous, oxygen-free nitrogen atmosphere, 301g of indium trichloride was added to a 903g indium trichloride ether solution. Then, 436g of trimethylindium was added to a 1281g trimethylindium ether solution. The indium trichloride ether solution was added to a 5L reactor, and then the trimethylindium ether solution was added dropwise while stirring, maintaining the reactor temperature at 40°C. After the addition was completed, the reactor was heated to reflux, and the reaction temperature was maintained at 40°C for 5 hours to obtain a dimethylindium chloride ether solution.

[0085] Under a nitrogen atmosphere, add 113g of magnesium chips and 994g of ether to another 5L reactor, take 497g of anhydrous N,N-dimethyl-3-chloropropylamine, add 20mL of N,N-dimethyl-3-chloropropylamine to the reactor, stir while heating, and turn off the heat when the reaction is initiated, the solution color becomes turbid, and the reaction reflux accelerates. Then, add the remaining N,N-dimethyl-3-chloropropylamine dropwise through a constant pressure funnel at a drop rate of 1s / drop, and control the reactor temperature at 40°C during the addition. After the addition is complete, maintain the reactor temperature at 40°C and heat under reflux for 4h. After the end, the Grignard reagent is obtained and cooled to room temperature for standby use.

[0086] The Grignard reagent was filtered and added dropwise to a dimethylindium chloride ether solution with stirring while adding dropwise. The reaction temperature was maintained at 60°C. After the addition was completed, the reactor temperature was maintained at 40°C for 4 hours. After the reaction was completed, the ether was distilled off at 34°C. After the system was cooled to room temperature, the fraction with a top temperature of 50-100°C / 4 mmHg was collected by vacuum distillation to obtain crude [3-(dimethylamino)propyl]dimethylindium.

[0087] The crude [3-(dimethylamino)propyl]dimethylindium was distilled through a distillation apparatus, the refrigerator temperature was set to 18±2°C, and the top temperature 55-59°C / 4mmHg fraction was collected to obtain 437g of pure [3-(dimethylamino)propyl]dimethylindium.

[0088] According to calculation, the yield of [3-(dimethylamino)propyl]dimethylindium in this embodiment is 46.3%, and the product is 1 The organic purity was 98.8% as determined by H NMR, and the inorganic purity reached 6N as determined by ICP-OES (inductively coupled plasma atomic emission spectrometry).

[0089] Example 5

[0090] A method for preparing [3-(dimethylamino)propyl]dimethylgallium comprises the following steps:

[0091] Under a nitrogen atmosphere, add 90g of magnesium chips and 800g of ether to a 5L reactor. Take 400g of anhydrous N,N-dimethyl-3-chloropropylamine and first add 20mL of N,N-dimethyl-3-chloropropylamine to the reactor. Stir while heating. Turn off the heat when the reaction is initiated, the solution becomes turbid, and the reaction reflux accelerates. Then, add the remaining N,N-dimethyl-3-chloropropylamine dropwise through a constant pressure funnel at a rate of 1 drop / s. The reactor temperature is controlled at 40°C during the addition. After the addition is complete, maintain the reactor temperature at 40°C and heat under reflux for 4h. After the end, the Grignard reagent is obtained and cooled to room temperature for later use.

[0092] Prepare 1332g of dimethylgallium chloride ether solution, containing 444g of dimethylgallium chloride. Filter the Grignard reagent and add it dropwise to the prepared dimethylgallium chloride ether solution with stirring. Maintain the reaction temperature at 50°C. After the addition is complete, maintain the reactor temperature at 40°C for 4 hours. After the reaction is complete, distill off the ether at 34°C. After the system cools to room temperature, perform vacuum distillation and collect the top temperature fraction at 50-100°C / 8 mmHg to obtain crude [3-(dimethylamino)propyl]dimethylgallium.

[0093] The crude [3-(dimethylamino)propyl]dimethylgallium product was distilled through a vacuum distillation apparatus and the top temperature fraction of 64-66°C / 7.5 mmHg was collected to obtain 275 g of pure [3-(dimethylamino)propyl]dimethylgallium with a yield of about 45%.

[0094] Product 1 The organic purity was 98.6% as determined by H NMR, and the inorganic purity was 6N as determined by ICP-OES (inductively coupled plasma atomic emission spectrometry).

[0095] Example 6

[0096] A method for preparing [3-(dimethylamino)propyl]dimethylaluminum comprises the following steps:

[0097] Under a nitrogen atmosphere, add 90g of magnesium chips and 800g of ether to a 5L reactor. Take 400g of anhydrous N,N-dimethyl-3-chloropropylamine and first add 20mL of N,N-dimethyl-3-chloropropylamine to the reactor. Stir while heating. Turn off the heat when the reaction is initiated, the solution becomes turbid, and the reaction reflux accelerates. Then, add the remaining N,N-dimethyl-3-chloropropylamine dropwise through a constant pressure funnel at a rate of 1 drop / s. The reactor temperature is controlled at 40°C during the addition. After the addition is complete, maintain the reactor temperature at 40°C and heat under reflux for 4h. After the end, the Grignard reagent is obtained and cooled to room temperature for later use.

[0098] Prepare 900g of dimethylaluminum chloride ether solution, containing 300g of dimethylaluminum chloride. Filter the Grignard reagent and add it dropwise to the prepared dimethylaluminum chloride ether solution while stirring. Maintain the reaction temperature at 50°C. After the addition is complete, maintain the reactor temperature at 40°C for 4 hours. After the reaction is completed, distill off the ether at 34°C. After the system is cooled to room temperature, distill under reduced pressure and collect the top temperature fraction of 50-100°C / 8mmHg to obtain crude [3-(dimethylamino)propyl]dimethylaluminum.

[0099] The crude [3-(dimethylamino)propyl]dimethylaluminum was distilled through a vacuum distillation apparatus and the top temperature fraction of 59-61°C / 3 mmHg was collected to obtain 215 g of pure [3-(dimethylamino)propyl]dimethylaluminum with a yield of about 46.3%.

[0100] Product 1 The organic purity was 98.7% as determined by H NMR, and the inorganic purity was 6N as determined by ICP-OES (inductively coupled plasma atomic emission spectrometry).

[0101] Example 7

[0102] A method for preparing [3-(dimethylamino)propyl]diethylgallium is as follows:

[0103] Under an anhydrous, oxygen-free nitrogen atmosphere, prepare 531g of a gallium trichloride n-hexane solution containing 177g of gallium trichloride and 942g of a triethylgallium n-hexane solution containing 314g of triethylgallium. Add the gallium trichloride n-hexane solution to a 2L reactor, then add the triethylgallium n-hexane solution dropwise while stirring, maintaining the reactor temperature at approximately 50°C. After the addition is complete, heat the reactor to reflux and maintain the reactor temperature at 50°C for 3 hours to produce a diethylgallium chloride n-hexane solution.

[0104] Under nitrogen, prepare a 2L reactor and add 81g of magnesium chips and 730g of n-hexane. Prepare 365g of anhydrous N,N-dimethyl-3-chloropropylamine. First, add 20mL of N,N-dimethyl-3-chloropropylamine. Then, heat and stir until the reaction is initiated, the solution becomes turbid, and the reflux rate accelerates. Then, turn off the heat and add the remaining N,N-dimethyl-3-chloropropylamine dropwise from the constant pressure funnel at a rate of 1s / drop. Keep the reactor temperature at 60°C during the addition. After the addition is complete, continue heating to maintain the system temperature at no less than 60°C and reflux for 2 hours to prepare the Grignard reagent. After the reaction is complete, turn off the heat and wait until the temperature returns to room temperature before preparing for the next step.

[0105] After filtering the above Grignard reagent, add it all dropwise into a 2L kettle containing diethylgallium chloride n-hexane solution, stirring while adding to maintain the reaction temperature not lower than 60°C. After all the addition is completed, continue stirring and maintain the kettle temperature not lower than 50°C for 2 hours.

[0106] In the 2L reactor used in the previous step, most of the solvent n-hexane was first distilled out at a temperature of 69-79°C, and then the fraction at 50-100°C / 4 mmHg was collected by reduced pressure distillation to obtain a crude product of [3-(dimethylamino)propyl]diethylgallium.

[0107] The crude [3-(dimethylamino)propyl]diethylgallium product was then distilled under reduced pressure on a distillation column. The fractions at 87-90°C / 7.5 mmHg were collected to obtain 104 g of the refined [3-(dimethylamino)propyl]diethylgallium product, with a yield of 48.6%. The product had an organic purity of 98.5% as determined by H NMR spectroscopy, and an inorganic purity of 6N as determined by ICP-OES.

[0108] Example 8

[0109] A method for preparing [3-(dimethylamino)propyl]dipropylindium is as follows:

[0110] Under an anhydrous, oxygen-free nitrogen atmosphere, prepare 675g of an indium trichloride n-hexane solution containing 225g of indium trichloride and 1470g of a tripropyl indium n-hexane solution containing 490g of tripropyl indium. First, add the indium trichloride n-hexane solution to a 2L reactor, then add the tripropyl indium n-hexane solution dropwise while stirring, maintaining the reactor temperature at approximately 50°C. After the addition is complete, heat the reactor to reflux and maintain the reactor temperature at 50°C for 3 hours to obtain a dipropyl indium chloride n-hexane solution.

[0111] Under nitrogen, prepare a 2L reactor and add 81g of magnesium chips and 730g of n-hexane. Prepare 365g of anhydrous N,N-dimethyl-3-chloropropylamine. First, add 20mL of N,N-dimethyl-3-chloropropylamine. Then, heat and stir until the reaction is initiated, the solution becomes turbid, and the reflux rate accelerates. Then, turn off the heat and add the remaining N,N-dimethyl-3-chloropropylamine dropwise from the constant pressure funnel at a rate of 1s / drop. Keep the reactor temperature at 60°C during the addition. After the addition is complete, continue heating to maintain the system temperature at no less than 60°C and reflux for 2 hours to prepare the Grignard reagent. After the reaction is complete, turn off the heat and wait until the temperature returns to room temperature before preparing for the next step.

[0112] After filtering the above Grignard reagent, add it all dropwise into a 2L kettle of dipropylindium chloride n-hexane solution, stirring while adding to maintain the reaction temperature not lower than 60°C. After all the addition is completed, continue stirring and maintain the kettle temperature not lower than 50°C for 2 hours.

[0113] In the 2L reactor used in the previous step, most of the solvent n-hexane was first distilled out at a temperature of 69-79°C, and then the fraction at 50-100°C / 4 mmHg was collected by reduced pressure distillation to obtain crude [3-(dimethylamino)propyl]dipropylindium.

[0114] The crude [3-(dimethylamino)propyl]dipropylindium product was then subjected to vacuum distillation on a rectification column with the refrigerator temperature set at 18±2°C. The fractions at 60-63°C / 0.04 mmHg were collected to obtain 139 g of fine [3-(dimethylamino)propyl]dipropylindium, with a yield of 48.4%. The product had an organic purity of 98.6% as determined by H NMR spectroscopy, and an inorganic purity of 6N as determined by ICP-OES.

[0115] In summary, the synthesis preparation method of the present invention is used to prepare Group III metal organic compounds for the semiconductor industry, specifically [3-(dimethylamino)propyl]dimethylindium, [3-(dimethylamino)propyl]dimethylgallium, [3-(dimethylamino)propyl]dimethylaluminum, [3-(dimethylamino)propyl]diethylgallium and [3-(dimethylamino)propyl]dipropylindium. The obtained finished products all have high purity, with an organic purity of up to 99% and an inorganic purity of up to 6N, which meets the purity requirements of the semiconductor industry. In addition, the preparation process is simple and easy to operate, the raw materials are widely available, and the cost is low.

[0116] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be included therein. Any reference sign in a claim should not be construed as limiting the claim to which it relates.

[0117] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing a group III metal organic compound for use in the semiconductor industry, characterized in that: include: R2MCl reacts with Grignard reagent (CH3)2N-(CH2)3-MgCl to obtain R2M-(CH2)3-N(CH3)2; wherein R is CH3, C2H5, C3H7 or i-C3H7; M is Ga or Al.

2. The method for preparing a group III metal organic compound for semiconductor industry according to claim 1, characterized in that: The steps include: Under an inert atmosphere, R3M reacts with MCl3 in a solvent to obtain R2MCl; Magnesium chips and (CH3)2N-(CH2)3-Cl are prepared into Grignard reagent in a solvent; R2MCl reacts with the above Grignard reagent and the solvent is removed to obtain a crude product of R2M-(CH2)3-N(CH3)2; The crude product was subjected to vacuum distillation to obtain the pure product.

3. The method for preparing a group III metal organic compound for semiconductor industry according to claim 2, characterized in that: The molar ratio of R3M and MCl3 is 2:

1.

4. The method for preparing a Group III metal organic compound for semiconductor industry according to claim 2, wherein: The usage ratio of R2MCl and Grignard reagent is calculated based on the molar ratio of MCl3 and (CH3)2N-(CH2)3-Cl, and the molar ratio of MCl3 and (CH3)2N-(CH2)3-Cl is 1:3-3.

05.

5. The method for preparing a Group III metal organic compound for semiconductor industry according to claim 2, characterized in that: When preparing R2MCl, the reaction temperature is 40-80°C and the reaction time is 3-6 hours; and / or, when preparing the Grignard reagent, the reaction temperature is 40-80°C and the reaction time is 2-4 hours; and / or, in the reaction of R2MCl and the Grignard reagent, the reaction temperature is 40-80°C and the reaction time is 3-6 hours.

6. The method for preparing a group III metal organic compound for semiconductor industry according to claim 2, characterized in that: When preparing R2MCl, R3M and solvent are mixed, MCl3 and solvent are mixed, and then the reaction is carried out; The mass ratio of R3M to solvent is 1:1.5-2.5; The mass ratio of MCl3 to solvent is 1:1.5-2.5; The solvent is one of n-hexane, diethyl ether and tetrahydrofuran.

7. The method for preparing a group III metal organic compound for semiconductor industry according to claim 2, characterized in that: After the reaction of R2MCl and Grignard reagent is completed, the solvent is distilled off, and the fraction with a top temperature of 55-100°C / 4 mmHg is collected by reduced pressure distillation to obtain a crude product.

8. The method for preparing a group III metal organic compound for semiconductor industry according to claim 2, characterized in that: During vacuum distillation, when R is CH3, if M is Ga, collect the fraction with a top temperature of 64-66°C / 7.5 mmHg; if M is Al, collect the fraction with a top temperature of 59-61°C / 3 mmHg; And / or, during vacuum distillation, when R is C2H5, if M is Ga, collect the fraction with a top temperature of 87-90°C / 7.5mmHg; if M is Al, collect the fraction with a top temperature of 103-106°C / 7.5mmHg; and / or, during vacuum distillation, when R is C3H7 and M is Ga, collecting the fraction with a top temperature of 96-99°C / 0.008 mmHg; And / or, during vacuum distillation, when R is i-C3H7, if M is Ga, collect the fraction with a top temperature of 85-87°C / 0.008 mmHg.

9. The method for preparing a Group III metal organic compound for semiconductor industry according to claim 2, characterized in that: The inert atmosphere was nitrogen.

10. The method for preparing a group III metal organic compound for semiconductor industry according to claim 2, characterized in that: When preparing the Grignard reagent, the molar ratio of magnesium turnings to (CH3)2N-(CH2)3-Cl is 1.1-1.2:1; And / or, when preparing the Grignard reagent, the mass ratio of the solvent to (CH3)2N-(CH2)3-Cl is 1.5-2.5:1.

Images