CN116008029A - Pretreatment method for analyzing trace impurities in high-purity ALD (atomic layer deposition) and CVD (chemical vapor deposition) precursors - Google Patents
Pretreatment method for analyzing trace impurities in high-purity ALD (atomic layer deposition) and CVD (chemical vapor deposition) precursors Download PDFInfo
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Abstract
A pretreatment method for analyzing trace impurities in high-purity ALD and CVD precursors comprises the steps of feeding a dry digestion tank and a sampling device which are accurately weighed into an inert atmosphere operation box, taking the precursors out by the sampling device, placing the precursors into the digestion tank, screwing a tank cover of the digestion tank, and taking out the inert atmosphere operation box. Accurately weighing the total weight of the digestion tank and the precursor in the digestion tank, heating in a hundred-grade ultra-clean workbench to evaporate and volatilize the precursor, slowly adding a first preset volume of concentrated acid along the wall for digestion, evaporating to be nearly dry, adding a second preset volume of concentrated acid for digestion after the reaction is finished, evaporating to be nearly dry, and dissolving substances in a sampling bottle by using a dilute acid solution with the solute mass percentage of 5% after the reaction is finished to prepare corresponding solution to be detected. The invention has the advantages of easy operation, good safety, short detection time, no environmental pollution, good repeatability of analysis results, wide applicability and the like.
Description
Technical Field
The invention relates to the technical field of chemical analysis, in particular to a pretreatment method for analyzing trace impurities in high-purity ALD (atomic layer deposition) and CVD (chemical vapor deposition) precursors.
Background
The precursor is used as a core manufacturing material of a semiconductor film deposition process, is a substance which has high barrier height and is applied to the semiconductor production and manufacturing process and carries target elements, gas or volatile liquid, has chemical heat stability and corresponding reactivity or physical properties. In semiconductor manufacturing processes including thin films, photolithography, interconnect, doping techniques, etc., precursors are mainly used in vapor deposition (including physical deposition PVD, chemical vapor deposition CVD, and atomic vapor deposition ALD) to form various thin film layers that meet the semiconductor manufacturing requirements. In addition, the precursor can also be used for semiconductor epitaxial growth, etching, ion implantation doping, cleaning and the like, and is one of core materials for semiconductor manufacture. Tetraethoxysilane (TEOS), for example, is used as a semiconductor silicon source for thin film deposition of doped and undoped silicon dioxide; tetra (dimethylamino) titanium (TDMAT) is a liquid phase chemical source suitable for chemical vapor deposition of titanium nitride films, which are effective diffusion barriers in semiconductor processing applications; triethylborate (TEB) is a liquid phase boron source for the deposition of Borosilicate (BSG) and Borophosphosilicate (BPSG) glass films in low pressure, atmospheric pressure, and plasma-enhanced CVD systems.
The high-purity ALD and CVD precursor products are core source materials of the whole electronic industry system, have extremely wide application in the fields of national defense and military industry, aerospace, novel solar cells and electronic products, and can ensure the quality requirements of product devices only by using more than 99.9999% (6N) precursor products. However, in the prior art, there is no pretreatment method for analyzing trace impurities in a semiconductor precursor.
Disclosure of Invention
In view of the above, the present invention provides a pretreatment method for analysis of trace impurities in high purity ALD, CVD precursors.
A pretreatment method for analysis of trace impurities in a high purity ALD, CVD precursor, comprising:
feeding the accurately weighed dry digestion tank and the sampling device into an inert atmosphere operation box, taking a precursor by the sampling device, placing the precursor into the digestion tank, then screwing a tank cover of the digestion tank, and taking out the inert atmosphere operation box;
accurately weighing the total weight of the digestion tank and the precursor in the digestion tank, heating in a hundred-grade ultra-clean workbench to evaporate and volatilize the precursor, slowly adding a first preset volume of concentrated acid along the wall for digestion, evaporating to be nearly dry, adding a second preset volume of concentrated acid for digestion after the reaction is finished, evaporating to be nearly dry, and dissolving substances in a sampling bottle by using a dilute acid solution with the solute mass percentage of 5% after the reaction is finished to prepare corresponding solution to be detected for subsequent detection.
According to the pretreatment method for analyzing the trace impurities in the high-purity ALD and CVD precursors, the sampling device is a liquid-state precursor at normal temperature, and the precursor is sucked by the liquid-state precursor and placed in the digestion tank.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors comprises the steps of Tetraethoxysilane (TEOS), octamethylcyclotetrasiloxane (OMCTS), tetramethylsilane (TMS), diethoxymethylsilane (DEMS), hexamethyldisilazane (HMDS), bis (tert-butylamino) silane (BTBAS), bis (diethylamino) silane (BDEAS), hexachlorodisilane (HCDS), titanium tetrachloride (TiCl 4), tetra (dimethylamino) titanium (TDMAT), triethyl phosphate (TEPO), trimethyl borate (TMB) and triethyl borate (TEB) or a mixture of a plurality of the precursors.
The pretreatment method for analyzing trace impurities in high-purity ALD (atomic layer deposition) and CVD (chemical vapor deposition) precursors, wherein the water content is kept to be less than 1ppm and the oxygen content is kept to be less than 1ppm in the inert atmosphere operation box; the inert atmosphere operation box is filled with inert gas, and the inert gas is nitrogen or helium.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors, wherein the weight of the precursor added into the digestion tank is 5-10 g. The precursor is stable in air and insoluble in water, only a few precursors are hydrolyzed when meeting water, and the sampling step is carried out in an inert atmosphere operation box with a sampling amount of 5-10 g, so that the precursor is not affected by micro hydrolysis in the heating evaporation process.
The pretreatment method for analyzing the trace impurities in the high-purity ALD and CVD precursors is characterized in that the heating is used for evaporating and volatilizing the major components of the precursors, so that the interference of the substrates during the subsequent detection is avoided.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors comprises the step of mixing one or more of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic 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, n-periodate, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid.
According to the pretreatment method for analyzing the trace impurities in the high-purity ALD and CVD precursors, the diluted acid with the mass percentage of 5% is prepared by diluting one or more mixed acids of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, chloric acid, metaphosphoric acid, hydrofluoric acid, selenic acid, fluoboric acid, fluorosulfonic acid, cyanic acid, thiocyanic acid, phosphoric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, pyrophosphoric acid, trifluoroacetic acid, phosphorous acid, n-periodate, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors comprises the step of completely using one or more mixed acids of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, chloric acid, hydrobromic 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, n-periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid when the precursor is one or a mixture of more of triethyl phosphate, trimethyl borate and triethyl borate.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors is characterized in that the precursor is one or a mixture of tetraethoxysilane, octamethyl cyclotetrasiloxane, tetramethylsilane, diethoxymethylsilane, hexamethyldisilazane, bis (tertiary butylamino) silane, bis (diethylamino) silane, hexachlorodisilane, titanium tetrachloride and tetra (dimethylamino) titanium, or is digested by using concentrated hydrofluoric acid or mixed acid of the concentrated hydrofluoric acid and other concentrated acids, wherein the other concentrated acids are one or a plurality of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, chloric acid, hydrobromic acid, metaphosphoric acid, selenoic 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, n-periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid.
According to the pretreatment method for analyzing the trace impurities in the high-purity ALD and CVD precursors, the temperature adopted during heating is 220 ℃ at most, the total heating time is not more than 1h, the heating process is carried out in a hundred-grade ultra-clean workbench, all gas emitted during heating is discharged by an exhaust fan and enters the exhaust gas treatment device through a pipeline, and no exhaust gas pollution is caused to the laboratory and outdoor environment.
The pretreatment method for analyzing trace impurities in high-purity ALD and CVD precursors, wherein the total operation process from the preparation of a sampling device to the completion of the decomposition of the precursor takes no more than 1.5 hours.
According to the pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors, the main components of the precursors are volatilized by adopting a volatilization method, and then concentrated acid is added to decompose the main components to form the soluble metal compounds, so that the pretreatment method has the advantages of easiness in operation, good safety, short detection time, no environmental pollution, good repeatability of analysis results, wide applicability and the like.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying examples in order to facilitate an understanding of the invention, however, the invention may be embodied in many different forms and is not limited to the examples described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, 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 belongs. 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.
The invention provides a pretreatment method for analyzing trace impurities in a high-purity ALD (atomic layer deposition) and CVD (chemical vapor deposition) precursor, which comprises the following steps of:
feeding the accurately weighed dry digestion tank and the sampling device into an inert atmosphere operation box, taking a precursor by the sampling device, placing the precursor into the digestion tank, then screwing a tank cover of the digestion tank, and taking out the inert atmosphere operation box;
accurately weighing the total weight of the digestion tank and the precursor in the digestion tank, heating in a hundred-grade ultra-clean workbench to evaporate and volatilize the precursor, slowly adding a first preset volume of concentrated acid along the wall for digestion, evaporating to be nearly dry, adding a second preset volume of concentrated acid for digestion after the reaction is finished, evaporating to be nearly dry, and dissolving substances in a sampling bottle by using a dilute acid solution with the solute mass percentage of 5% after the reaction is finished to prepare corresponding solution to be detected for subsequent detection.
The pretreatment method for analyzing trace impurities in high-purity ALD (atomic layer deposition) and CVD (chemical vapor deposition) precursors, wherein the sampling device is a pipette.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors comprises the step of carrying out pretreatment on the precursor, wherein the precursor is one or a mixture of more of tetraethoxysilane, octamethyl cyclotetrasiloxane, tetramethylsilane, diethoxymethylsilane, hexamethyldisilazane, bis (tertiary butylamino) silane, bis (diethylamino) silane, hexachlorodisilane, titanium tetrachloride, tetra (dimethylamino) titanium, triethyl phosphate, trimethyl borate and triethyl borate.
The pretreatment method for analyzing trace impurities in high-purity ALD (atomic layer deposition) and CVD (chemical vapor deposition) precursors, wherein the water content is kept to be less than 1ppm and the oxygen content is kept to be less than 1ppm in the inert atmosphere operation box; the inert atmosphere operation box is filled with inert gas, and the inert gas is nitrogen or helium.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors, wherein the weight of the precursor added into the digestion tank is 5-10 g.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors comprises the step of mixing one or more of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic 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, n-periodate, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid.
According to the pretreatment method for analyzing the trace impurities in the high-purity ALD and CVD precursors, the diluted acid with the mass percentage of 5% is prepared by diluting one or more mixed acids of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, chloric acid, metaphosphoric acid, hydrofluoric acid, selenic acid, fluoboric acid, fluorosulfonic acid, cyanic acid, thiocyanic acid, phosphoric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, pyrophosphoric acid, trifluoroacetic acid, phosphorous acid, n-periodate, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors comprises the step of completely using one or more mixed acids of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, chloric acid, hydrobromic 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, n-periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid when the precursor is one or a mixture of more of triethyl phosphate, trimethyl borate and triethyl borate.
The pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors is characterized in that the precursor is one or a mixture of tetraethoxysilane, octamethyl cyclotetrasiloxane, tetramethylsilane, diethoxymethylsilane, hexamethyldisilazane, bis (tertiary butylamino) silane, bis (diethylamino) silane, hexachlorodisilane, titanium tetrachloride and tetra (dimethylamino) titanium, or is digested by using concentrated hydrofluoric acid or mixed acid of the concentrated hydrofluoric acid and other concentrated acids, wherein the other concentrated acids are one or a plurality of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, chloric acid, hydrobromic acid, metaphosphoric acid, selenoic 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, n-periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid.
According to the pretreatment method for analyzing the trace impurities in the high-purity ALD and CVD precursors, the temperature adopted during heating is 220 ℃ at most, the total heating time is not more than 1h, the heating process is carried out in a hundred-grade ultra-clean workbench, and all gases emitted during heating are discharged by an exhaust fan and enter an exhaust gas treatment device through a pipeline.
The following examples are provided to further illustrate embodiments of the invention. The embodiments of the present invention are not limited to the following specific embodiments. The modification can be appropriately performed within the scope of the main claim.
Example 1
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, keeping the oxygen content in the inert atmosphere operation box between 0.3 and 0.6ppm, taking 10mL of triethyl borate into the digestion tank by using the pipettor, then screwing a bottle cap of the digestion tank, and taking out the inert atmosphere operation box. The total weight of the digestion tank and the triethyl borate therein was accurately weighed on an analytical balance so that the weight of the triethyl borate in the digestion tank was about 9g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of concentrated nitric acid along the wall for digestion, evaporating to near dryness, adding 1mL of concentrated nitric acid for digestion after the reaction is finished, and evaporating to near dryness.
And (3) dissolving substances in the sampling bottle by using a nitric acid solution with the solute mass percent of 5% to prepare a corresponding solution to be detected for detection. Wherein the ratio of substance/nitric acid solution in digestion tank = 1g/mL. The instrument uses inductively coupled plasma mass spectrometry ICP MS.
And (5) sampling by using a mass spectrum standard solution containing metal elements. Recording the signal intensity of the element to be detected in the standard solution. And (3) repeatedly measuring each standard solution at least three times until the relative standard deviation of the intensity values measured in parallel for three times is not more than 3%, taking an average value, and drawing a standard curve which takes the signal intensity of the element to be measured as an ordinate and the concentration of the element to be measured as an abscissa.
And (3) feeding a blank solution (a triethyl borate sample is not added in a sample bottle, the rest steps are the same as those of the sample solution) under the same measurement conditions as those of the sample solution to be measured, recording the signal intensities of different elements to be measured, repeatedly measuring for at least three times until the relative deviation of the parallel measurement values of the intensities of the three times is not more than 3%, and taking an average value.
And (3) detecting the content of the element to be detected in the solution to be detected on a corresponding metal element standard curve by using the measured signal intensity of the element to be detected in the solution to be detected, calculating the content of the corresponding element to be detected in the blank solution by the same method, and respectively calculating the content of the corresponding element to be detected in the triethyl borate according to the following formula, wherein the result is shown in the table 1. Wherein the calculation formula is as follows:
wherein:
w represents the content of an element to be detected in triethyl borate, and the unit is micrograms per gram (mug/g);
w 1 the content of the element to be detected in the solution to be detected is expressed in micrograms per milliliter (mug/ml);
w 0 representing the content of the element to be detected in the blank solutionIn micrograms per milliliter (μg/ml);
v represents the volume of the solution to be measured in milliliters (mL);
m represents the sampling mass of triethyl borate in grams (g).
TABLE 1
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Si(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.005 | 0.002 | 0.007 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.004 | 0.001 | 0.008 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.004 | 0.001 | 0.007 | ≤0.001 |
As is clear from the table above, the content of trace impurities in the triethyl borate measured by the method of the present example was excellent in reproducibility and stable in results.
Example 2
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, keeping the oxygen content in the inert atmosphere operation box between 0.3 and 0.6ppm, taking 10mL of triethyl phosphate into the digestion tank by using the pipettor, then screwing a bottle cap of the digestion tank, and taking out the inert atmosphere operation box. The total weight of the digestion tank and the triethyl phosphate therein was accurately weighed on an analytical balance so that the weight of triethyl phosphate in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of concentrated nitric acid along the wall for digestion, evaporating to near dryness, adding 1mL of concentrated nitric acid for digestion after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a nitric acid solution with the solute mass percent of 5% to prepare a corresponding solution to be detected for detection.
The apparatus was prepared using inductively coupled plasma mass spectrometry ICPMS, the test and calculation method was exactly the same as in example 1, and the results of three determinations of triethyl phosphate samples are shown in Table 2:
TABLE 2
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Si(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.007 | ≤0.001 | 0.003 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.006 | ≤0.001 | 0.004 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.006 | ≤0.001 | 0.004 | ≤0.001 |
As is clear from the table, the content of trace impurities in the triethyl phosphate measured by the method of the example is good in repeatability and stable in result.
Example 3
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, keeping the oxygen content in the inert atmosphere operation box between 0.3 and 0.6ppm, taking 10mL trimethyl borate into the digestion tank by using the pipettor, then screwing a bottle cap of the digestion tank, and taking out the inert atmosphere operation box. The total weight of the digestion tank and trimethyl borate therein was accurately weighed on an analytical balance such that the trimethyl borate weight in the digestion tank was about 9g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of mixed acid of concentrated hydrochloric acid and concentrated nitric acid along the wall to digest, evaporating to near dryness, adding 1mL of mixed acid of concentrated hydrochloric acid and concentrated nitric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a nitric acid solution with the solute mass percent of 5% to prepare corresponding solution to be detected for detection.
The apparatus was prepared using inductively coupled plasma mass spectrometry ICPMS, the test and calculation method was exactly the same as in example 1, and the results of three measurements of trimethyl borate samples are shown in Table 3:
TABLE 3 Table 3
As is clear from the above table, the content of trace impurities in trimethyl borate measured by the method of the example is good in repeatability, and the result is stable.
Example 4
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 10mL of tetra (dimethylamino) titanium into the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and the tetra (dimethylamino) titanium therein was accurately weighed on an analytical balance such that the tetra (dimethylamino) titanium weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of concentrated hydrofluoric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness.
And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection. Wherein the ratio of the substance/hydrofluoric acid solution in the digestion tank=1 g/mL. The instrument uses inductively coupled plasma mass spectrometry ICP MS.
And (5) sampling by using a mass spectrum standard solution containing metal elements. Recording the signal intensity of the element to be detected in the standard solution. And (3) repeatedly measuring each standard solution at least three times until the relative standard deviation of the intensity values measured in parallel for three times is not more than 3%, taking an average value, and drawing a standard curve which takes the signal intensity of the element to be measured as an ordinate and the concentration of the element to be measured as an abscissa.
And (3) feeding a blank solution (a sample bottle is not added with a tetra (dimethylamino) titanium sample, the rest steps are the same as those of the sample solution) and the sample solution to be measured under the same measuring conditions as those of a standard measuring solution, recording the signal intensities of different elements to be measured, repeatedly measuring at least three times until the relative deviation of the parallel measured values of the intensities of the three times is not more than 3%, and taking an average value.
The content of the element to be measured in the solution to be measured is found out on the corresponding metal element standard curve by using the measured signal intensity of the element to be measured in the solution to be measured, the content of the corresponding element to be measured in the blank solution calculated by the same method is calculated, the content of the corresponding element to be measured in tetra (dimethylamino) titanium is calculated according to the following formula, and the result is shown in table 4. Wherein the calculation formula is as follows:
wherein:
w represents the content of an element to be detected in (dimethylamino) titanium, and the unit is micrograms per gram (mug/g);
w 1 the content of the element to be detected in the solution to be detected is expressed in micrograms per milliliter (mug/ml);
w 0 the content of the element to be detected in the blank solution is expressed in micrograms per milliliter (mug/ml);
v represents the volume of the solution to be measured in milliliters (mL);
m represents the sampling mass of tetra (dimethylamino) titanium in grams (g).
TABLE 4 Table 4
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Si(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.003 | ≤0.001 | 0.010 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.003 | ≤0.001 | 0.011 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.004 | ≤0.001 | 0.011 | ≤0.001 |
As can be seen from the table, the analysis result of the trace impurity content in the tetra (dimethylamino) titanium measured by the method of the embodiment has the advantages of good repeatability, good applicability and the like.
Example 5
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 6mL of titanium tetrachloride into the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and the titanium tetrachloride therein was precisely weighed on an analytical balance such that the titanium tetrachloride weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of concentrated hydrofluoric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection.
The apparatus was prepared using inductively coupled plasma mass spectrometry ICPMS, the test and calculation method was exactly the same as in example 4, and the three measurements of titanium tetrachloride samples are shown in Table 5:
TABLE 5
As can be seen from the table, the analysis result of the trace impurity content in the titanium tetrachloride measured by the method of the embodiment has the advantages of good repeatability, good applicability and the like.
Example 6
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 10mL of tetraethoxysilane into the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and tetraethoxysilane therein was accurately weighed on an analytical balance such that the tetraethoxysilane weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of concentrated hydrofluoric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness.
And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection. Wherein the ratio of the substance/hydrofluoric acid solution in the digestion tank=1 g/mL. The instrument uses inductively coupled plasma mass spectrometry ICP MS.
And (5) sampling by using a mass spectrum standard solution containing metal elements. Recording the signal intensity of the element to be detected in the standard solution. And (3) repeatedly measuring each standard solution at least three times until the relative standard deviation of the intensity values measured in parallel for three times is not more than 3%, taking an average value, and drawing a standard curve which takes the signal intensity of the element to be measured as an ordinate and the concentration of the element to be measured as an abscissa.
And (3) sampling a blank solution (a tetraethoxysilane sample is not added in a sample bottle, the rest steps are the same as those of the sample solution) and the sample solution to be measured under the same measurement conditions as those of a standard measurement solution, recording the signal intensities of different elements to be measured, repeatedly measuring for at least three times until the relative deviation of the parallel measurement values of the intensities of the three times is not more than 3%, and taking an average value.
And (3) detecting the content of the element to be detected in the solution to be detected on the corresponding metal element standard curve by using the measured signal intensity of the element to be detected in the solution to be detected, calculating the content of the corresponding element to be detected in the blank solution by the same method, and respectively calculating the content of the corresponding element to be detected in tetraethoxysilane according to the following formula, wherein the result is shown in Table 6. Wherein the calculation formula is as follows:
wherein:
w represents the content of the element to be detected in tetraethoxysilane, and the unit is micrograms per gram (mug/g);
w 1 the content of the element to be detected in the solution to be detected is expressed in micrograms per milliliter (mug/ml);
w 0 the content of the element to be detected in the blank solution is expressed in micrograms per milliliter (mug/ml);
v represents the volume of the solution to be measured in milliliters (mL);
m represents the sampling mass of tetraethoxysilane in grams (g).
TABLE 6
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Mn(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.012 | ≤0.001 | 0.010 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.013 | ≤0.001 | 0.010 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.013 | ≤0.001 | 0.011 | ≤0.001 |
As can be seen from the table, the tetraethoxysilane prepared by the method has the advantages of good repeatability of analysis results of trace impurity content in tetraethoxysilane, good applicability and the like.
Example 7
Feeding the precisely weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 10mL of octamethyl cyclotetrasiloxane into the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and the octamethyltetrasiloxane therein was accurately weighed on an analytical balance such that the octamethyltetrasiloxane weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of concentrated hydrofluoric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection.
The apparatus was prepared using inductively coupled plasma mass spectrometry ICPMS, and the test and calculation methods were exactly the same as in example 6, and the results of three measurements on octamethyl cyclotetrasiloxane samples are shown in Table 7:
TABLE 7
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Mn(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.011 | 0.004 | 0.008 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.010 | 0.005 | 0.008 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.011 | 0.005 | 0.009 | ≤0.001 |
As can be seen from the table, the analysis result of the content of the trace impurities in the octamethyl cyclotetrasiloxane measured by the method of the embodiment has the advantages of good repeatability, good applicability and the like.
Example 8
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 15mL of tetramethylsilane in the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and the tetramethylsilane therein was accurately weighed on an analytical balance such that the tetramethylsilane weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of concentrated hydrofluoric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection.
The apparatus was prepared using inductively coupled plasma mass spectrometry ICPMS, and the test and calculation methods were exactly the same as in example 6, and the results of three determinations of tetramethylsilane samples are shown in Table 8:
TABLE 8
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Mn(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.011 | 0.003 | 0.011 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.012 | 0.002 | 0.012 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.012 | 0.003 | 0.011 | ≤0.001 |
As can be seen from the table, the method for measuring the content of the trace impurities in the tetramethylsilane has the advantages of good repeatability, good applicability and the like.
Example 9
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 13mL of hexamethyldisilazane in the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and hexamethyldisilazane therein was accurately weighed on an analytical balance such that the hexamethyldisilazane weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, then slowly adding 2mL of concentrated hydrofluoric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection.
The apparatus was prepared using inductively coupled plasma mass spectrometry ICPMS, and the test and calculation methods were exactly the same as in example 6, and the results of three measurements on hexamethyldisilazane samples are shown in Table 9:
TABLE 9
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Mn(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.011 | 0.006 | 0.009 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.010 | 0.006 | 0.010 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.012 | 0.005 | 0.009 | ≤0.001 |
As can be seen from the table, the analysis result of the content of the trace impurity in the hexamethyldisilazane, which is measured by the method of the embodiment, has the advantages of good repeatability, good applicability and the like.
Example 10
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 12mL of diethoxymethylsilane into the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and the diethoxymethylsilane therein was accurately weighed on an analytical balance such that the diethoxymethylsilane weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, slowly adding 2mL of mixed acid of concentrated hydrofluoric acid and nitric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection.
The apparatus was prepared using inductively coupled plasma mass spectrometry ICPMS, and the test and calculation methods were exactly the same as in example 6, and the results of three determinations of diethoxymethylsilane samples are shown in Table 10:
table 10
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Mn(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.011 | ≤0.001 | 0.007 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.011 | ≤0.001 | 0.007 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.012 | ≤0.001 | 0.006 | ≤0.001 |
As can be seen from the above table, the analysis result of the content of trace impurities in the diethoxymethylsilane measured by the method of the present embodiment has the advantages of good repeatability, good applicability and the like.
Example 11
The accurately weighed dry digestion tank and a pipettor are sent into an inert atmosphere operation box, the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and 12mL of bis (tertiary butyl amino) silane is taken in the digestion tank by the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and bis (t-butylamino) silane therein was accurately weighed on an analytical balance such that the bis (t-butylamino) silane weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, slowly adding 2mL of mixed acid of concentrated hydrofluoric acid and nitric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection.
The apparatus was run using inductively coupled plasma mass spectrometry ICPMS, and the test and calculation methods were exactly the same as in example 6, with three measurements of bis (t-butylamino) silane samples as shown in Table 11:
TABLE 11
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Mn(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.011 | 0.005 | 0.009 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.012 | 0.004 | 0.008 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.012 | 0.004 | 0.009 | ≤0.001 |
As can be seen from the above table, the analysis result of the content of trace impurities in the bis (tertiary butylamino) silane measured by the method of the present embodiment has the advantages of good repeatability, good applicability and the like.
Example 12
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 12mL of bis (diethylamino) silane into the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and the bis (diethylamino) silane therein was accurately weighed on an analytical balance such that the bis (diethylamino) silane weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, slowly adding 2mL of mixed acid of concentrated hydrofluoric acid and nitric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection.
The apparatus was run using inductively coupled plasma mass spectrometry ICPMS, and the test and calculation methods were exactly the same as in example 6, with three measurements of bis (diethylamino) silane samples as shown in Table 12:
table 12
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Mn(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.010 | 0.008 | 0.009 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.010 | 0.008 | 0.010 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.009 | 0.007 | 0.009 | ≤0.001 |
As can be seen from the above table, the analysis result of the content of trace impurities in the bis (diethylamino) silane measured by the method of the present embodiment has the advantages of good repeatability, good applicability and the like.
Example 13
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, wherein the oxygen content in the inert atmosphere operation box is maintained between 0.3 and 0.6ppm, and taking 7mL of hexachlorodisilane in the digestion tank by using the pipettor. And then the digestion tank cover is screwed down, and the inert atmosphere operation box is taken out. The total weight of the digestion tank and hexachlorodisilane therein was accurately weighed on an analytical balance such that the hexachlorodisilane weight in the digestion tank was about 10g. Then heating in a hundred-grade ultra-clean workbench to evaporate and volatilize, slowly adding 2mL of mixed acid of concentrated hydrofluoric acid and nitric acid along the wall to digest, evaporating to near dryness, adding 1mL of concentrated hydrofluoric acid to digest after the reaction is finished, and evaporating to near dryness. And (3) dissolving substances in the sampling bottle by using a hydrofluoric acid solution with the solute mass percent of 5%, and preparing a corresponding solution to be detected for detection.
The apparatus was prepared using inductively coupled plasma mass spectrometry ICPMS, and the test and calculation methods were exactly the same as in example 6, and the results of three measurements of hexachlorodisilane samples are shown in Table 13:
TABLE 13
| Impurity element | Cu(μg/g) | Fe(μg/g) | Mg(μg/g) | Mn(μg/g) | Zn(μg/g) |
| Results of the first test | ≤0.001 | 0.014 | 0.006 | 0.012 | ≤0.001 |
| Results of the second test | ≤0.001 | 0.014 | 0.007 | 0.013 | ≤0.001 |
| Results of the third test | ≤0.001 | 0.013 | 0.007 | 0.012 | ≤0.001 |
As can be seen from the table, the analysis result of the content of trace impurities in hexachlorodisilane, which is measured by the method in the embodiment, has the advantages of good repeatability, good applicability and the like.
In addition, in the implementation cases of respectively adopting one or more of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, chloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, metaphosphoric acid, hydrofluoric acid, selenic acid, fluoboric acid, fluosulfonic acid, cyanic acid, thiocyanic acid, phosphoric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, pyrophosphoric acid, trifluoroacetic acid, phosphorous acid, n-periodate, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid, citric acid and the like to respectively digest the trace impurity content in the triethyl phosphate, trimethyl borate and triethyl borate, the measured contents of the triethyl phosphate, trimethyl borate and the triethyl borate all meet the requirements and the repeatability is good.
In the embodiment of adopting hydrofluoric acid to digest tetraethoxysilane, octamethyl cyclotetrasiloxane, tetramethylsilane, diethoxymethylsilane, hexamethyldisilazane, bis (tertiary butylamino) silane, bis (diethylamino) silane, hexachlorodisilane, titanium tetrachloride and tetra (dimethylamino) titanium, the content of the trace impurities in the precursor sample is measured to meet the requirements and the repeatability is good.
In the embodiment of the precursor sample, the content of trace impurities in the precursor sample is required to be met and the repeatability is good, wherein the trace impurities are obtained by respectively digesting tetraethoxysilane, octamethyl cyclotetrasiloxane, tetramethylsilane, diethoxymethylsilane, hexamethyldisilazane, bis (tertiary butylamino) silane, bis (diethylamino) silane, hexachlorodisilane, titanium tetrachloride and tetra (dimethylamino) titanium with one or more of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, selenic acid, fluoroboric acid, hydrobromic acid, metaphosphoric 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, n-periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid, citric acid and the like.
Comparative example
And (3) feeding the accurately weighed dry digestion tank and the pipettor into an inert atmosphere operation box, taking 2mL of tetra (dimethylamino) titanium into the digestion tank by using the pipettor, then screwing a bottle cap of the digestion tank, and taking out the inert atmosphere operation box. The total weight of the digestion tank and the precursor therein was accurately weighed on an analytical balance such that the precursor weight in the digestion tank was about 2g.
The sampling rules and the safety are in accordance with the regulations of the sampling rule of solid chemical products (GB/T6679) and the sampling safety rule of industrial chemical products (GB/T3723). Loosening the opening of the digestion tank to naturally oxidize the precursor in the tank for 120 hours. Adding 2mL of hydrofluoric acid into a digestion tank for digestion after oxidation, heating to dissolve the materials, slowly adding 1mL of hydrofluoric acid solution with the solute percentage by mass of 5% along the wall for digestion after volatilizing and evaporating to dryness, evaporating to be near dryness, and preparing a corresponding solution to be detected by using the hydrofluoric acid solution with the solute percentage by mass of 5% after the reaction is finished.
Experiments find that there are three aspects of the process:
1. the decomposition reaction time is long, which is not beneficial to the detection requirement of multi-batch production;
2. part of the precursor is easy to form different crystals in the slow oxidation process, and can not be completely dissolved, so that the analysis result is deviated;
3. the precursor in the digestion tank is decomposed and oxidized naturally, so that the direct discharge can pollute the environment, and the tail gas is required to be treated additionally.
In conclusion, the pretreatment method for analyzing trace impurities in the high-purity ALD and CVD precursors provided by the invention adopts a volatilization method to volatilize main components of the precursors, and then adds concentrated acid to decompose the main components to form soluble metal compounds, and has the advantages of easiness in operation, good safety, short detection time, no environmental pollution, good repeatability of analysis results, wide applicability and the like.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A pretreatment method for analysis of trace impurities in a high purity ALD, CVD precursor, comprising:
feeding the accurately weighed dry digestion tank and the sampling device into an inert atmosphere operation box, taking a precursor by the sampling device, placing the precursor into the digestion tank, then screwing a tank cover of the digestion tank, and taking out the inert atmosphere operation box;
accurately weighing the total weight of the digestion tank and the precursor in the digestion tank, heating in a hundred-grade ultra-clean workbench to evaporate and volatilize the precursor, slowly adding a first preset volume of concentrated acid along the wall for digestion, evaporating to be nearly dry, adding a second preset volume of concentrated acid for digestion after the reaction is finished, evaporating to be nearly dry, and dissolving substances in a sampling bottle by using a dilute acid solution with the solute mass percentage of 5% after the reaction is finished to prepare corresponding solution to be detected for subsequent detection.
2. The pretreatment method for analysis of trace impurities in high purity ALD, CVD precursors of claim 1, wherein the sampling device is a pipette.
3. The pretreatment method for analysis of trace impurities in high purity ALD, CVD precursors of claim 1, wherein the precursor is one or a mixture of tetraethoxysilane, octamethylcyclotetrasiloxane, tetramethylsilane, diethoxymethylsilane, hexamethyldisilazane, bis (t-butylamino) silane, bis (diethylamino) silane, hexachlorodisilane, titanium tetrachloride, tetra (dimethylamino) titanium, triethyl phosphate, trimethyl borate, triethyl borate.
4. The pretreatment method for analysis of trace impurities in high purity ALD, CVD precursors of claim 1, wherein the inert atmosphere operation box maintains a water content of less than 1ppm and an oxygen content of less than 1ppm; the inert atmosphere operation box is filled with inert gas, and the inert gas is nitrogen or helium.
5. The pretreatment method for analysis of trace impurities in high purity ALD, CVD precursors of claim 1, wherein the precursor added to the digestion tank weighs between 5 and 10g.
6. The pretreatment method for analyzing trace impurities in high-purity ALD and CVD precursors according to claim 1, wherein the concentrated acid is one or more of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, perbromic acid, chloric acid, hydrobromic acid, metaphosphoric acid, hydrofluoric acid, selenoic 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, n-periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid, citric acid.
7. The pretreatment method for analyzing trace impurities in high-purity ALD and CVD precursors according to claim 1, wherein the diluted acid with the solute mass percentage of 5% is prepared by diluting one or more mixed acids of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, chloric acid, bromic acid, metaphosphoric acid, hydrofluoric acid, selenoic 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, n-periodate, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid.
8. The pretreatment method for analyzing trace impurities in high-purity ALD and CVD precursors according to claim 1, wherein when the precursor is one or a mixture of several of triethyl phosphate, trimethyl borate and triethyl borate, the precursor is digested with one or several mixed acids of nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, hydrobromic 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, n-periodate, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid and citric acid.
9. The pretreatment method for analysis of trace impurities in high purity ALD, CVD precursors according to claim 1, wherein the precursor is one or more of tetraethoxysilane, octamethylcyclotetrasiloxane, tetramethylsilane, diethoxymethylsilane, hexamethyldisilazane, bis (t-butylamino) silane, bis (diethylamino) silane, hexachlorodisilane, titanium tetrachloride, tetra (dimethylamino) titanium, digested with concentrated hydrofluoric acid, or a mixed acid of concentrated hydrofluoric acid and other concentrated acids selected from nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, perbromic acid, chloric acid, hydrobromic acid, metaphosphoric acid, selenoic 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, n-periodic acid, maleic acid, nitrous acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, benzenesulfonic acid, citric acid.
10. The pretreatment method for analyzing trace impurities in high purity ALD and CVD precursors according to claim 1, wherein the temperature used for heating is 220 ℃ at most, the total heating time is no more than 1h, the heating process is performed in a hundred-stage ultra clean bench, all the gas emitted during heating is exhausted from an exhaust fan, and the gas is introduced into an exhaust gas treatment device through a pipe.
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