Pretreatment method for analyzing trace impurities in trimethyl indium

Abstract

The invention provides a pretreatment method for analyzing trace impurities in trimethyl indium, which comprises the following steps: taking trimethyl indium in an inert atmosphere operation box by adopting a sampling device, placing the trimethyl indium in a dry sampling bottle, sealing the dry sampling bottle to obtain a metal organic compound, and taking the dry sampling bottle out of the inert atmosphere operation box; weighing the total weight of the dry sampling bottle and the metal organic compound, and adding a water-insoluble organic solvent into the dry sampling bottle on a hundred-grade super clean bench, so that the organic solvent reacts with the metal organic compound to obtain a first solution; adding a first dilute acid solution into the dry sampling bottle, reacting concentrated acid with the first solution, and heating to remove alkane to obtain a second solution; and adding a second dilute acid solution into the second solution in the dry sampling bottle to prepare a solution to be detected. The method has the advantages of being easy to operate, good in safety, short in detection time, free of environmental pollution, good in analysis result repeatability, wide in applicability and the like.

Description

Technical Field

[0001] This invention relates to the field of chemical analysis technology, and in particular to a pretreatment method for the analysis of trace impurities in trimethylindium. Background Technology

[0002] Organometallic compounds are a crucial raw material for epitaxial growth, but they are chemically highly reactive, exploding upon contact with water and burning upon contact with oxygen. Therefore, they must be decomposed into mild inorganic compounds in a specific atmosphere before they can be introduced into the instrument for impurity element determination.

[0003] In the prior art, invention patent CN102103049A discloses a trimethylaluminum HCl decomposition device for the analysis of trace impurities in trimethylaluminum, providing a method for the elemental analysis of trace impurities in trimethylaluminum by decomposing it with HCl. The advantage of using hydrogen chloride gas for decomposition is that it solves the problems of long decomposition reaction time and incomplete dissolution of different crystals, which can cause deviations in analytical results. However, the preparation process of hydrogen chloride gas is complex, and the prepared hydrogen chloride gas may also contain other trace impurities, which can easily lead to deviations in the analysis of organometallic compound products requiring a purity greater than 99.9995%. Summary of the Invention

[0004] Therefore, the purpose of this invention is to provide a pretreatment method for the analysis of trace impurities in trimethylindium, so as to overcome the shortcomings of the prior art.

[0005] This invention provides a pretreatment method for the analysis of trace impurities in trimethylindium, the method comprising: The accurately weighed dry sampling bottle and sampling device are sent into an inert atmosphere operating chamber. The sampling device is used to take trimethylindium in the inert atmosphere operating chamber and place it in the dry sampling bottle. The dry sampling bottle is then sealed to obtain an organometallic compound. The dry sampling bottle is then removed from the inert atmosphere operating chamber. Weigh the total weight of the dried sampling bottle and the organometallic compound, and add an organic solvent insoluble in water to the dried sampling bottle on a Class 100 clean bench to allow the organic solvent to react with the organometallic compound to obtain a first solution; A first dilute acid solution is added to the dried sampling bottle, and the concentrated acid reacts with the first solution. The mixture is then heated to remove alkanes, yielding a second solution. A second dilute acid solution is added to the second solution in the dried sampling bottle to prepare the solution to be tested.

[0006] Compared with the prior art, the beneficial effects of the present invention are: by using an organic solvent and a 5% dilute acid solution to decompose the organic compound trimethylindium to form a soluble oxide, it has the advantages of being easy to operate, safe, having a short detection time, not polluting the environment, having good repeatability of analytical results, and being widely applicable.

[0007] Furthermore, the sampling device is a pipette or a stainless steel sampling spoon.

[0008] Furthermore, the water content and oxygen content in the inert atmosphere operating chamber are less than 1 ppm, and the inert gas in the inert atmosphere operating chamber is nitrogen or helium.

[0009] Furthermore, the trimethylindium weighs between 0.1 g and 0.3 g.

[0010] Furthermore, the organic solvent is 0.5 mL to 0.6 mL.

[0011] Furthermore, the organic solvent is one or a mixture of several of the following organic solvents: n-pentane, isopentane, neopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, cycloheptane, n-octane, petroleum ether, carbon tetrachloride, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, pentachloroethane, benzene, or toluene.

[0012] Furthermore, the first and second dilute acid solutions each have a solute mass percentage of 5%.

[0013] Furthermore, the first and second dilute acid solutions are prepared by diluting one or more of the following acids: nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, perbromic acid, chloric acid, bromic acid, metaphosphoric acid, hydrofluoric acid, selenic acid, fluoroboric acid, fluorosulfonic acid, cyanic acid, thiocyanic acid, phosphoric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, pyrophosphoric acid, trifluoroacetic acid, phosphorous acid, periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid, or citric acid.

[0014] Furthermore, the heating temperature is ≤140℃, and the heating time is 9min~11min.

[0015] Furthermore, the step of heating to react and release toxic gases includes: The concentrated acid and the first solution are heated inside the Class 100 clean bench, and the toxic gas is discharged to the waste gas treatment device through the exhaust fan. Detailed Implementation

[0016] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0019] Example 1 The pretreatment method for trace impurity analysis in diethyltelluride according to the first embodiment of the present invention includes steps S1 to S4: S1, the accurately weighed dry sampling bottle and sampling device are sent into an inert atmosphere operating chamber, the sampling device is used to take trimethylindium in the inert atmosphere operating chamber and place it in the dry sampling bottle, and the dry sampling bottle is sealed to obtain an organometallic compound, and the dry sampling bottle is taken out from the inert atmosphere operating chamber. In this embodiment, the sampling device is a stainless steel sampling spoon. Trimethylindium is solid at room temperature. The solid is taken into a sampling bottle using the stainless steel sampling spoon. Trimethylindium is then taken into the sampling bottle using the stainless steel sampling spoon, and the bottle cap is tightened before removing the inert atmosphere operating chamber. The oxygen content in the inert atmosphere operating chamber is between 0.3 ppm and 0.6 ppm, the water content is maintained between 0.2 ppm and 0.5 ppm, and the inert gas in the inert atmosphere operating chamber is nitrogen. S2, Weigh the total weight of the dried sampling bottle and the organometallic compound, and add an organic solvent insoluble in water to the dried sampling bottle on a Class 100 clean bench to allow the organic solvent to react with the organometallic compound to obtain a first solution; It should be noted that the total weight of the sampling bottle and the trimethylindium contained therein was accurately measured on the analytical balance, ensuring that the weight of trimethylindium in the sampling bottle was approximately 0.1 g. Then, 0.5 mL of n-pentane was quickly added to the sampling bottle on a Class 100 cleaning table to thoroughly mix the sample. Ultrapure water was then slowly added dropwise to allow the reaction to proceed. Because trimethylindium reacts violently with water, generating high heat and releasing flammable gases, and can ignite and explode upon contact with oxygen, a sample volume of 0.1–0.3 g is used. Adding an organic solvent that is insoluble in water can reduce its miscibility and activity. Adding ultrapure water further reduces the extent of the reaction.

[0020] It is worth noting that trimethylindium spontaneously combusts upon contact with air, reacting completely to produce indium trioxide, carbon dioxide, and water, etc. The reaction equation is as follows: 2(CH3)3In+12O2=In2O3+9H2O+6CO2; Trimethylindium reacts violently with water, releasing flammable gases that can cause combustion and explosion, producing Me₂InOH and [(Me₂In)₂O]. x The intermediate products react completely to form indium hydroxide and release methane gas. The reaction equation is as follows: (CH3)3In+3H2O=In(OH)3+3CH4.

[0021] S3, add a first dilute acid solution to the dried sampling bottle, and react the concentrated acid with the first solution, and heat to remove alkanes to obtain a second solution; It should be noted that after the reaction is complete, add 5% nitric acid solution (mass percentage of solute) to fully dissolve the sample, and then heat to remove n-pentane.

[0022] In this embodiment, the heating temperature is 140°C and the heating time is 10 minutes. During heating, the concentrated acid and the first solution are heated in the Class 100 clean bench, and the toxic gas is discharged from the exhaust fan to the waste gas treatment device to avoid environmental pollution.

[0023] S4, add a second dilute acid solution to the second solution in the dried sampling bottle to prepare the test solution.

[0024] It should be noted that the content of the corresponding analyte in trimethylindium was determined according to the requirements of the national standard GB / T37030 2018, using a 5% nitric acid solution as the analyte solution for detection. The ratio of the substance in the sampling vial to the nitric acid solution was 10 mg / mL. Inductively coupled plasma mass spectrometry (ICP-MS) was used.

[0025] Inject the sample using a mass spectrometry standard solution containing a metal element. Record the signal intensity of the analyte in the standard solution. Each standard solution should be measured at least three times until the relative standard deviation of the intensity values ​​from the three parallel measurements is no greater than 3%. Take the average value and plot a standard curve with the signal intensity of the analyte as the ordinate and the concentration of the analyte as the abscissa.

[0026] Inject the blank solution (without adding trimethylindium sample to the sample vial, and the remaining steps are the same as for the sample solution) and the test sample solution under the same measurement conditions as for the standard solution. Record the signal intensity of different test elements. Repeat the measurement at least three times until the relative deviation of the three parallel intensity measurements is no greater than 3%, and take the average value.

[0027] The content of the analyte in the test solution was determined by analyzing the signal intensity of the analyte in the test solution against the corresponding metal element standard curve. The content of the corresponding analyte in the blank solution was calculated using the same method. The content of the corresponding analyte in trimethylindium was then calculated using the following formula, and the results are shown in Table 1. The calculation formula is: ; In the formula, This indicates the content of the analyte element in trimethylindium, expressed in micrograms per gram (μg / g). This indicates the content of the element to be tested in the solution. This indicates the concentration of the element to be tested in the blank solution, expressed in micrograms per milliliter (μg / ml). The volume of the solution being tested is expressed in milliliters (mL). The sample mass of trimethylindium is expressed in grams (g). Table 1

[0028] As shown in Table 1, the method described in this embodiment yields good repeatability and stable results for the determination of trace impurities in trimethylindium.

[0029] Example 2 The pretreatment method for analyzing trace impurities in trimethylindium in the second embodiment of the present invention differs from the pretreatment method for analyzing trace impurities in trimethylindium in the first embodiment in that: Precisely weighed, dried sampling vials and a stainless steel sampling spoon were placed in an inert atmosphere chamber, where the oxygen content was maintained between 0.3 and 0.6 ppm. Trimethylindium was transferred into the sampling vial using the stainless steel sampling spoon, and the vial cap was tightened before removing the chamber. The total weight of the sampling vial and the trimethylindium contained therein was accurately measured on an analytical balance, ensuring that the weight of trimethylindium in the vial was approximately 0.1 g. Then, 0.5 mL of n-hexane was quickly added to the sampling vial on a Class 100 cleaning table to thoroughly mix the sample. Ultrapure water was then slowly added dropwise to allow the reaction to proceed. After the reaction was complete, a 5% nitric acid solution was added to fully dissolve the sample, and the hexane was removed by heating. The corresponding test solution was then prepared using a 5% nitric acid solution for analysis.

[0030] The instrument used was inductively coupled plasma mass spectrometry (ICP-MS). The testing and calculation methods were exactly the same as in Example 1. Table 2 shows the results of three determinations of the trimethylindium sample: Table 2

[0031] As shown in Table 2, the method described in this embodiment yields good repeatability and stable results for the determination of trace impurities in trimethylindium.

[0032] Example 3 The pretreatment method for analyzing trace impurities in trimethylindium in the third embodiment of this invention differs from the pretreatment methods in the previous embodiments in that: A precisely weighed, dried sampling bottle and a stainless steel sampling spoon are placed in an inert atmosphere chamber, where the oxygen content is maintained between 0.3 and 0.6 ppm. Trimethylindium is scooped into the sampling bottle using the stainless steel sampling spoon, and the bottle cap is tightened. The inert atmosphere chamber is then removed. The total weight of the sampling bottle and the trimethylindium contained therein is precisely weighed on an analytical balance, ensuring that the weight of trimethylindium in the sampling bottle is approximately 0.1 g. Then, 0.5 mL of n-pentane is quickly added to the sampling bottle on a Class 100 cleaning table to thoroughly mix the sample. Ultrapure water is then slowly added dropwise to allow the reaction to proceed. After the reaction is complete, a 5% hydrochloric acid solution is added to fully dissolve the sample, and the n-hexane is removed by heating. The corresponding test solution was prepared using a 5% hydrochloric acid solution.

[0033] The instrument used was inductively coupled plasma mass spectrometry (ICP-MS). The testing and calculation methods were exactly the same as in Example 1. Table 3 shows the results of three determinations of the trimethylindium sample: Table 3

[0034] As shown in Table 3, the method described in this embodiment yields good repeatability and stable results for the determination of trace impurities in trimethylindium.

[0035] In other alternative embodiments, trimethylindium is selected from one or a mixture of several organic solvents insoluble in water, including n-pentane, isopentane, neopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,4-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, cycloheptane, n-octane, petroleum ether, carbon tetrachloride, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, pentachloroethane, benzene, and toluene. In other alternative embodiments, the first and second dilute acid solutions are prepared by diluting one or more of the following acids: nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, perbromic acid, chloric acid, bromic acid, metaphosphoric acid, hydrofluoric acid, selenic acid, fluoroboric acid, fluorosulfonic acid, cyanic acid, thiocyanic acid, phosphoric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, pyrophosphoric acid, trifluoroacetic acid, phosphorous acid, periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid, or citric acid.

[0036] It should be noted that the total time spent in implementing the above embodiments did not exceed 0.5 hours; the total time from adding the organic solvent to preparing the test solution did not exceed 15 minutes.

[0037] Example 4 The pretreatment method for analyzing trace impurities in trimethylindium in the fourth embodiment of this invention differs from the pretreatment methods in the previous embodiments in that: A precisely weighed, dried sampling bottle and a stainless steel sampling spoon are placed in an inert atmosphere chamber, where the oxygen content is maintained between 0.3 and 0.6 ppm. Trimethylindium is scooped into the sampling bottle using the stainless steel sampling spoon, and the bottle cap is tightened. The inert atmosphere chamber is then removed. The total weight of the sampling bottle and the trimethylindium contained therein is precisely weighed on an analytical balance, ensuring that the weight of trimethylindium in the sampling bottle is approximately 0.2 g. Then, 0.5 mL of n-pentane is quickly added to the sampling bottle on a Class 100 cleaning table to thoroughly mix the sample. Ultrapure water is then slowly added dropwise to allow the reaction to proceed. After the reaction is complete, a 5% hydrochloric acid solution is added to fully dissolve the sample, and the n-hexane is removed by heating. The corresponding test solution was prepared using a 5% hydrochloric acid solution.

[0038] The instrument used was inductively coupled plasma mass spectrometry (ICP-MS). The testing and calculation methods were exactly the same as in Example 1. Table 4 shows the results of three determinations of the trimethylindium sample: Table 4

[0039] As shown in Table 4, the method described in this embodiment yields good repeatability and stable results for the determination of trace impurities in trimethylindium.

[0040] Example 5 The pretreatment method for analyzing trace impurities in trimethylindium in the fifth embodiment of this invention differs from the pretreatment methods in the previous embodiments in that: A precisely weighed, dried sampling bottle and a stainless steel sampling spoon are placed in an inert atmosphere chamber, where the oxygen content is maintained between 0.3 and 0.6 ppm. Trimethylindium is scooped into the sampling bottle using the stainless steel sampling spoon, and the bottle cap is tightened before removing the inert atmosphere chamber. The total weight of the sampling bottle and the trimethylindium contained therein is precisely weighed on an analytical balance, ensuring that the weight of trimethylindium in the sampling bottle is approximately 0.3 g. Then, 0.5 mL of n-pentane is quickly added to the sampling bottle on a Class 100 cleaning table to thoroughly mix the sample. Ultrapure water is then slowly added dropwise to allow the reaction to proceed. After the reaction is complete, a 5% hydrochloric acid solution is added to fully dissolve the sample, and the n-hexane is removed by heating. The corresponding test solution was prepared using a 5% hydrochloric acid solution.

[0041] The instrument used was inductively coupled plasma mass spectrometry (ICP-MS). The testing and calculation methods were exactly the same as in Example 1. Table 5 shows the results of three determinations of the trimethylindium sample: Table 5

[0042] As shown in Table 5, the method described in this embodiment yields good repeatability and stable results for the determination of trace impurities in trimethylindium.

[0043] Comparative Example The precisely weighed, dry sampling bottle and stainless steel sampling spoon were placed into an inert atmosphere operating chamber. Trimethylindium was transferred into the sampling bottle using the stainless steel sampling spoon. The bottle cap was then tightened, and the inert atmosphere operating chamber was removed. The total weight of the sampling bottle and the trimethylindium contained therein was accurately measured on an analytical balance, ensuring that the weight of trimethylindium in the sampling bottle was approximately 0.1 g.

[0044] Sampling rules and safety procedures shall comply with the provisions of the "General Rules for Sampling of Solid Chemical Products" (GB / T 6679) and the "General Safety Rules for Sampling of Industrial Chemical Products" (GB / T 3723). Loosen the mouth of the sampling bottle to allow the organometallic compounds in the bottle to oxidize naturally for 24 hours. Then, prepare the corresponding test solution using a 5% (w / w) nitric acid solution for detection.

[0045] The experiment revealed three problems with this process: the decomposition reaction time is long, which is not conducive to the testing of multiple batches of production; some metal-organic sources are prone to forming different crystals during the slow oxidation process, which cannot be completely dissolved, causing deviations in the analysis results; the decomposition and natural oxidation process of metal-organic sources in the sampling bottle may cause environmental pollution if directly discharged, requiring additional treatment of the exhaust gas.

[0046] In summary, the pretreatment method for the analysis of trace impurities in trimethylindium in the above embodiments of the present invention, which uses an organic solvent and a 5% dilute acid solution to decompose the organic compound trimethylindium to form a soluble oxide, has the advantages of being easy to operate, safe, having a short detection time, not polluting the environment, having good repeatability of analytical results, and being widely applicable.

[0047] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0048] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A pretreatment method for the analysis of trace impurities in trimethylindium, characterized in that, The method includes: The accurately weighed dry sampling bottle and sampling device are sent into an inert atmosphere operating chamber. The sampling device is used to take trimethylindium in the inert atmosphere operating chamber and place it in the dry sampling bottle. The dry sampling bottle is then sealed to obtain an organometallic compound. The dry sampling bottle is then removed from the inert atmosphere operating chamber. Weigh the total weight of the dried sampling bottle and the organometallic compound, and add an organic solvent insoluble in water to the dried sampling bottle on a Class 100 clean bench to allow the organic solvent to react with the organometallic compound to obtain a first solution; A first dilute acid solution is added to the dried sampling bottle, and the concentrated acid reacts with the first solution. The mixture is then heated to remove alkanes, yielding a second solution. A second dilute acid solution is added to the second solution in the dried sampling bottle to prepare the solution to be tested.

2. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The sampling device is a pipette or a stainless steel sampling spoon.

3. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The inert atmosphere operating chamber contains less than 1 ppm of water and less than 1 ppm of oxygen, and the inert gas in the inert atmosphere operating chamber is nitrogen or helium.

4. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The trimethylindium weighs between 0.1 g and 0.3 g.

5. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The organic solvent is 0.5 mL to 0.6 mL.

6. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The organic solvent is one or a mixture of several of the following organic solvents: n-pentane, isopentane, neopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, cycloheptane, n-octane, petroleum ether, carbon tetrachloride, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, pentachloroethane, benzene, or toluene.

7. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The first and second dilute acid solutions each have a solute mass percentage of 5%.

8. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The first and second dilute acid solutions are prepared by diluting one or more of the following acids: nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, perbromic acid, chloric acid, bromic acid, metaphosphoric acid, hydrofluoric acid, selenic acid, fluoroboric acid, fluorosulfonic acid, cyanic acid, thiocyanic acid, phosphoric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, pyrophosphoric acid, trifluoroacetic acid, phosphorous acid, periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid, or citric acid.

9. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The heating temperature is ≤140℃, and the heating time is 9min~11min.

10. The pretreatment method for trace impurity analysis in trimethylindium according to claim 1, characterized in that, The step of heating to react and release toxic gases includes: The concentrated acid and the first solution are heated inside the Class 100 clean bench, and the toxic gas is discharged to the waste gas treatment device through the exhaust fan.

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