JP2016125911A - Element analysis method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an element analysis method capable of analyzing impurity elements in a sample including a silicon containing compound with accuracy 1,000 times compared with conventional one while preventing an element analyzer from being blocked by the deposition of a silicon matrix.SOLUTION: The method for analyzing impurity elements in a sample including a silicon containing compound comprises: decomposing the silicon containing compound included in the sample using an automatic vapor phase decomposition apparatus including at least a heating mechanism, a liquid sending mechanism and a conveyance mechanism; removing a silicon part in the sample after the decomposition to prepare a sample for element analysis; automatically injecting the prepared sample for element analysis into the element analyzer; and analyzing impurity elements in the sample for element analysis.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for analyzing an impurity element in a sample containing a silicon-containing compound, and in particular, a silicon-containing film used in a semiconductor device manufacturing process such as a silicon-containing resist underlayer film forming material or an interlayer insulating film forming material. The present invention relates to a method for analyzing an impurity element in a forming coating material.

  Along with the high integration and high speed of LSI, the circuit pattern dimension is rapidly miniaturized. Along with this miniaturization, the lithography technology has achieved the formation of a fine pattern by shortening the wavelength of the light source and appropriately selecting the resist composition corresponding thereto.

  However, in the case of miniaturization with the same light source, if only the pattern width is reduced without changing the film thickness of the photoresist film to be used, the aspect ratio of the photoresist pattern after development increases, resulting in pattern collapse. There was a problem. For this reason, the photoresist film thickness has been reduced with the miniaturization so that the aspect ratio of the photoresist pattern falls within an appropriate range. However, with the thinning of the photoresist film, the problem of substrate processing failure due to insufficient dry etching resistance further occurred.

  One method for solving such problems is a multilayer resist method. In this method, a lower layer film having different etching selectivity from a photoresist film (that is, a resist upper layer film) is interposed between the resist upper layer film and the substrate to be processed, and after obtaining a pattern on the resist upper layer film, the upper layer resist pattern is formed. This is a method of transferring a pattern to a lower layer film by dry etching as a dry etching mask, and further transferring the pattern to a substrate to be processed by dry etching using the lower layer film as a dry etching mask.

  In recent years, a silicon-containing resist underlayer film has been used as a resist underlayer film in such a multilayer resist method (Patent Document 1). Since the silicon-containing resist underlayer film is easy to form and has an etching selectivity different from that of the resist upper layer film, it has excellent processing performance. However, in recent years, particularly in a fine semiconductor process after the 32 nm / 28 nm node, a metal element contained as an impurity in the resist underlayer film can become a dry etching mask and cause a short circuit or disconnection of a semiconductor device circuit. Have been found. For this reason, removal of the impurity element contained in the silicon-containing resist underlayer film forming material is required.

  Generally, when a sample containing a silicon-containing compound is injected into an elemental analyzer, the sample is diluted to an appropriate concentration with a solvent in the same manner as a normal organic compound and injected into a high-sensitivity elemental analyzer such as ICP-MS. The silicon content inside is oxidized to form a silicon matrix (composite consisting mainly of silicon dioxide), which deposits on the vacuum interface and further progresses to clog the part, impairing the reproducibility of the measurement. However, there was a problem of inducing a failure of the elemental analyzer. Thus, especially when the sample contains a silicon-containing compound, it is difficult to quantify the impurity element contained in the sample, and therefore, the technology for removing the impurity element cannot be differentiated. This has hindered progress in technology to reduce impurities in such materials.

JP 2007-302873 A

  As a countermeasure against such problems, conventionally, in order to prevent clogging of the elemental analyzer due to precipitation of the silicon matrix, the sample is diluted on a large scale, for example, about 100 to 1,000 times with a clean solvent. However, it has been practiced to minimize the amount of silicon matrix deposited in the elemental analyzer. However, in such a method, the sample is diluted in a large scale, so that a trace amount of metal elements mixed as impurities are also diluted, so that the mass is high enough to show sensitivity that can be quantitatively detected by elemental analysis. There is a problem that the impurity element cannot be introduced, and only detection sensitivity of about 500 ppt (0.5 ppb) can be obtained.

  The present invention has been made in order to solve the above-described problems. The impurity element in a sample containing a silicon-containing compound is reduced 1,000 times as much as that of the conventional one while preventing clogging of the elemental analyzer due to deposition of a silicon matrix. It is an object of the present invention to provide an elemental analysis method capable of analyzing with high accuracy.

  In order to solve the above-described problems, the present invention is a method for analyzing an impurity element in a sample containing a silicon-containing compound, and includes an automatic vapor decomposition apparatus provided with at least a heating mechanism, a liquid feeding mechanism, and a conveying mechanism. Is used to decompose the silicon-containing compound contained in the sample, remove the silicon content in the sample after decomposition, prepare a sample for elemental analysis, and automatically analyze the prepared elemental analysis sample for elemental analysis Provided is an elemental analysis method for injecting into an apparatus and analyzing an impurity element in the elemental analysis sample.

  With such an elemental analysis method, it occurs when a sample containing a silicon-containing compound is injected into a conventional elemental analyzer by decomposing the silicon-containing compound in the sample and performing a pretreatment to remove the silicon content. The precipitation of the silicon matrix derived from the silicon content in the sample can be prevented. For this reason, it is introduced directly into an elemental analysis apparatus such as ICP-MS in the same manner as a general analysis sample without performing large-scale dilution of a sample that has been conventionally performed to suppress the influence of silicon matrix precipitation. As a result, the impurity element can be analyzed with an accuracy of 0.5 ppt, which is 1,000 times higher than that of the prior art.

At this time, in the automatic gas phase decomposition apparatus,
(1) A step of adding any one of nitric acid and hydrofluoric acid or a mixture thereof to the sample,
(2) a step of decomposing the silicon-containing compound in the sample by either or both of ozone gas treatment and heat treatment;
(3) heat-treating the sample after decomposition, evaporating and removing the silicon content in the sample after decomposition, and (4) dissolving the sample from which the silicon content has been removed in an acid,
It is preferable to prepare a sample for elemental analysis by automatically performing the above.

  By performing such a process, a sample for elemental analysis from which silicon contained in the sample is removed can be more efficiently prepared.

  At this time, the sample may be concentrated or evaporated to dryness by heat treatment at 30 ° C. or more and 300 ° C. or less before the step (1). By concentrating or evaporating to dryness in this way, the solvent or the like originally contained in the sample can be removed, and gas phase decomposition can be performed more reliably.

  At this time, nitric acid, hydrofluoric acid, or a mixture thereof may be added before and after any of the steps (1) to (4).

  At this time, the heat treatment in the step (2) is preferably performed at 30 ° C. or higher and 300 ° C. or lower. By performing the heat treatment at such a temperature, the silicon-containing compound in the sample can be decomposed more effectively.

  At this time, the heat treatment in the step (3) is preferably performed at 35 ° C. or higher and 350 ° C. or lower. By performing heat treatment at such a temperature, the silicon content in the sample after decomposition can be more effectively removed by evaporation.

  At this time, the acid used in the step (4) is preferably nitric acid or hydrofluoric acid, or a mixture thereof. With such an acid, the sample from which the silicon content has been removed can be more reliably dissolved.

  At this time, the sample may be a coating material for forming a silicon-containing film used in the semiconductor device manufacturing process. The sample may contain a silane monomer or a polymer compound containing a silicon atom in a repeating unit, particularly a polysiloxane compound. The sample may be an aqueous solution or an organic solvent solution of the silicon-containing compound. The elemental analysis method of the present invention is particularly suitable for the analysis of impurity elements in such samples.

  The elemental analyzer is preferably any one of an inductively coupled plasma mass spectrometer, an inductively coupled plasma emission analyzer, and an atomic absorption spectrometer. By using such an element analyzer, the impurity element can be analyzed with higher accuracy.

  Moreover, it is preferable to use what was equipped with the ozone gas processing unit as said automatic vapor phase decomposition apparatus.

As described above, according to the elemental analysis method of the present invention, the impurity element in the sample containing the silicon-containing compound can be detected with a precision 1000 times that of the conventional one while preventing the clogging of the elemental analyzer due to the precipitation of the silicon matrix. Quantitative analysis can be performed with a certain accuracy of 0.5 ppt. Accordingly, a silicon-containing film used in an ultrafine semiconductor process after a 20 nm node, such as a silicon-containing resist underlayer film forming material or an interlayer insulating film forming material, which is required to detect a minute amount of impurity elements with high accuracy. It is particularly suitable for analysis of impurity elements in the forming coating material.
When such elemental analysis method of the present invention is applied to the management of metal impurities in the silicon-containing resist underlayer film forming material, it becomes possible to suppress defects generated during dry etching, and a dry etching process is used. Pattern transfer without defects is possible. As a result, the yield of semiconductor device manufacturing can be improved finally. Further, when the elemental analysis method of the present invention is applied to the management of metal impurities in the material for forming an interlayer insulating film, the withstand voltage characteristics of the insulating film can be improved. This ultimately contributes to improving the performance of the semiconductor device.

It is the schematic which shows an example of the automatic vapor phase decomposition apparatus used for the elemental analysis method of this invention.

  As described above, development of an elemental analysis method capable of analyzing impurity elements in a sample containing a silicon-containing compound with 1,000 times the accuracy of the conventional one while preventing clogging of the elemental analyzer due to deposition of a silicon matrix. Was demanded.

  As a result of intensive studies on the above problems, the present inventors have conducted a pretreatment for decomposing a silicon-containing compound in a sample and removing a silicon component while maintaining a clean state, and thus a conventional elemental analyzer has silicon. It has been found that the precipitation of the silicon matrix derived from the silicon content in the sample, which has occurred when the sample containing the containing compound is injected, can be prevented. This also eliminates the need for large-scale dilution of the sample, which has been performed in order to suppress the influence of silicon matrix precipitation, resulting in an accuracy of 0.5 ppt, which is 1,000 times higher than the conventional accuracy. The inventors have found that it is possible to analyze impurity elements and have completed the present invention.

  That is, the present invention is a method for analyzing an impurity element in a sample containing a silicon-containing compound, the sample using an automatic gas phase decomposition apparatus equipped with at least a heating mechanism, a liquid feeding mechanism, and a conveying mechanism. Decomposing the silicon-containing compound contained therein, removing the silicon content in the sample after decomposition, preparing a sample for elemental analysis, automatically injecting the prepared sample for elemental analysis into the elemental analyzer, It is an elemental analysis method for analyzing an impurity element in the elemental analysis sample.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

First, an automatic vapor decomposition apparatus used in the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing an example of an automatic gas phase decomposition apparatus used in the elemental analysis method of the present invention.
The automatic vapor phase decomposition apparatus 1 of FIG. 1 includes a mechanism for transporting a sample in a sample container 4 set on a carbon plate 3 by a robot arm 2 to each unit for physicochemical treatment in a clean environment. . In addition, as a unit for physicochemical treatment, an acid feeding unit 5 that feeds acid for decomposition treatment, ozone gas that performs ozone gas treatment (ozone decomposition treatment) with ozone gas supplied from a gas feeding mechanism in the decomposition chamber A treatment unit 6 and a heat treatment unit 7 for performing heat treatment in the heating chamber are provided. Further, a sample injection port 8 for injecting a sample into the sample container 4 and an element analysis sample liquid feeding unit 9 for injecting an element analysis sample prepared by performing each process into the element analysis device are provided.

  The carbon plate 3 is preferably coated with a fluorocarbon resin, and the sample container 4 is preferably made of a fluorocarbon resin. The robot arm 2 and each processing unit are preferably installed in a clean chamber whose cleanliness is controlled by, for example, ISO class 3.

  Further, in such an automatic gas phase decomposition apparatus 1, processing order such as processing order in each processing unit (acid feeding unit 5, ozone gas processing unit 6, and heat processing unit 7) by software, processing conditions such as processing temperature, It is possible to control the type of acid used. As a result, it is possible to automatically perform a pretreatment for appropriately decomposing the silicon-containing compound in the sample and removing the silicon content in the sample that causes a failure of the elemental analyzer.

  An example of the operation of the automatic gas phase decomposition apparatus 1 used in the present invention is shown below. First, the sample container 4 is set on the carbon plate 3 set on the sample injection port 8, and the sample is injected into the sample container 4. Next, the carbon plate 3 is moved to each processing unit (the acid feeding unit 5, the ozone gas processing unit 6, and the heating processing unit 7) by the robot arm 2 in accordance with the pre-programmed order and conditions. To decompose the silicon-containing compound in the sample, remove the silicon content in the sample, and prepare a sample for elemental analysis. When the preparation is completed, the robot arm 2 moves the carbon plate 3 to the element analysis sample feeding unit 9 and automatically injects the prepared element analysis sample into the element analysis apparatus.

  As an elemental analysis apparatus used in the present invention, an inductively coupled plasma-mass spectrometer (ICP-MS), an inductively coupled plasma emission spectrometer (ICP-MS), an inductively coupled plasma emission spectrometer (ICP-MS) is used. It is preferable to use any one of an atomic absorption spectrometer (AAS) as a detection device. By using such an element analyzer, the impurity element can be analyzed with higher accuracy.

Next, the elemental analysis method of the present invention will be described in detail.
In the elemental analysis method of the present invention, first, a silicon-containing compound contained in a sample is decomposed using an automatic vapor phase decomposition apparatus equipped with at least a heating mechanism, a liquid feeding mechanism, and a conveying mechanism as described above. Then, the silicon content in the sample after decomposition is removed to prepare a sample for elemental analysis. Thereafter, the prepared element analysis sample is automatically injected into the element analysis apparatus as described above, and the impurity element in the element analysis sample is analyzed.

At this time, specifically, it is preferable to prepare a sample for elemental analysis by automatically performing the following steps in the automatic gas phase decomposition apparatus.
(1) Step of adding nitric acid or hydrofluoric acid or a mixture thereof to the sample (2) Step of decomposing the silicon-containing compound in the sample by ozone gas treatment and / or heat treatment (3 ) A step of heat-treating the sample after decomposition and evaporating and removing the silicon content in the sample after decomposition (4) A step of dissolving the sample from which the silicon content has been removed in an acid

Hereinafter, each step will be described in more detail.
[(1) Process]
In the step (1), either nitric acid or hydrofluoric acid or a mixture thereof is added to the sample. At this time, addition of nitric acid and hydrofluoric acid or a mixture thereof may be divided into two or more times. Moreover, it does not specifically limit as nitric acid and hydrofluoric acid used at this time, For example, a 0.1-50 mass% thing is respectively preferable.

  In addition, you may concentrate or evaporate and dry a sample by heat-processing at 30 to 300 degreeC before a (1) process. By concentrating or evaporating to dryness in this way, the solvent or the like originally contained in the sample can be removed, and gas phase decomposition can be performed more reliably.

[(2) Process]
In the step (2), the silicon-containing compound in the sample is decomposed by ozone gas treatment and / or heat treatment.
When performing ozone gas processing, although it does not specifically limit, For example, it is preferable to process for 1 to 100 minutes, flowing ozone gas 0.1-100 mL / min.
Moreover, when performing heat processing, it is preferable to carry out at 30 to 300 degreeC. By performing the heat treatment at such a temperature, the silicon-containing compound in the sample can be decomposed more effectively. The time for the heat treatment is not particularly limited, but for example, it is preferably 1 to 600 minutes.

[(3) Process]
(3) In the step, the decomposed sample is heat-treated, and the silicon content in the decomposed sample is evaporated and removed. Note that the heat treatment at this time is preferably performed at 35 ° C to 350 ° C. By performing heat treatment at such a temperature, the silicon content in the sample after decomposition can be more effectively removed by evaporation. The time for the heat treatment is not particularly limited, but for example, it is preferably 1 to 600 minutes.

[(4) Process]
(4) In the step, the sample from which silicon has been removed is dissolved in acid. The acid used at this time is preferably nitric acid or hydrofluoric acid, or a mixture thereof. With such an acid, the sample from which the silicon content has been removed can be more reliably dissolved. Moreover, it does not specifically limit as nitric acid and hydrofluoric acid used at this time, For example, a 0.1-50 mass% thing is respectively preferable.

  Moreover, you may add nitric acid, a hydrofluoric acid, or these mixtures before and after the process in any one of (1)-(4). In addition, although it does not specifically limit as nitric acid and hydrofluoric acid used at this time, For example, a 0.1-50 mass% thing is respectively preferable.

  By performing the steps as described above, a sample for elemental analysis from which the silicon content contained in the sample has been removed can be prepared more efficiently.

  The sample to be subjected to the elemental analysis method of the present invention is not particularly limited as long as it contains a silicon-containing compound. For example, a semiconductor device manufacturing process such as a silicon-containing resist underlayer film forming material or an interlayer insulating film forming material The coating material for forming a silicon-containing film used in (1) can be mentioned. Examples of the material for forming the interlayer insulating film include those described in JP 2009-286935 A, for example.

  In the present invention, the silicon-containing compound is not particularly limited as long as it is a compound containing a silicon atom. Examples of such a silicon-containing compound include a silicon-containing monomer such as a silane monomer, and a polymer compound containing a silicon atom in a repeating unit such as a polysiloxane compound. Examples of the polysiloxane compound include those described in JP-A-2007-302873. The polymer compound containing a silicon atom in the repeating unit may not have a siloxane structure. Examples of such a polymer compound are described in JP-A-2004-027210. Can be exemplified. Moreover, 1 type may be sufficient as the silicon containing compound contained in a sample, and 2 or more types may be sufficient as it. More specifically, the sample may include only one of a monomer and a polymer compound, or may include both a monomer and a polymer compound. The sample may be an aqueous solution or an organic solvent solution of a silicon-containing compound.

  In the present invention, the “impurity element” specifically refers to an element that is said to affect the yield of a process when a semiconductor device is manufactured. As this element, Li, Be, B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, Sn, Sb, Ba, La, Ce, Nd, Sm, Eu, Gd, Hf, Ta, W, Ir, Pt, Au, Tl , Pb, Bi and the like. Among these, elements that are particularly problematic in the semiconductor device manufacturing process include Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Pd, Examples thereof include Ag, Cd, Sn, Ba, W, Au, and Pb. Further, since there is a possibility of becoming a dry etching mask after dry etching processing, elements that may be problematic include Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Examples include Cd, Sn, Ba, W, Au, Pb.

  Since the elemental analysis method of the present invention can measure such elements with an accuracy of 0.5 ppt, silicon-containing compounds such as a silicon-containing resist underlayer film forming material and an interlayer insulating film forming material can be used. It becomes possible to control the amount (content rate) of the impurity element in the contained material.

As described above, according to the elemental analysis method of the present invention, the impurity element in the sample containing the silicon-containing compound can be detected with a precision 1000 times that of the conventional one while preventing the clogging of the elemental analyzer due to the precipitation of the silicon matrix. Quantitative analysis can be performed with a certain accuracy of 0.5 ppt. Accordingly, a silicon-containing film used in an ultrafine semiconductor process after a 20 nm node, such as a silicon-containing resist underlayer film forming material or an interlayer insulating film forming material, which is required to detect a minute amount of impurity elements with high accuracy. It is particularly suitable for analysis of impurity elements in the forming coating material.
When such elemental analysis method of the present invention is applied to the management of metal impurities in the silicon-containing resist underlayer film forming material, it becomes possible to suppress defects generated during dry etching, and a dry etching process is used. Pattern transfer without defects is possible. As a result, the yield of semiconductor device manufacturing can be improved finally. Further, when the elemental analysis method of the present invention is applied to the management of metal impurities in the material for forming an interlayer insulating film, the withstand voltage characteristics of the insulating film can be improved. This ultimately contributes to improving the performance of the semiconductor device.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to these.

[Example 1]
The following operations were performed using the automatic vapor decomposition apparatus shown in FIG. 1 and an elemental analysis apparatus (7700s (ICP-MS) manufactured by Agilent Technologies) connected thereto.
A 5 mL sample container made of fluorocarbon resin was set on a carbon plate coated with fluorocarbon resin set on the sample injection port. Into this sample container, 0.5 mL of a propylene glycol ethyl ether (PGEE) solution containing polysiloxane represented by the following formula at a concentration of 10% by mass was injected.
The following operations were programmed in advance and operated automatically. First, with the robot arm, the sample container was moved to the heat treatment unit while being mounted on the carbon plate, and the sample was evaporated to dryness by heat treatment at 120 ° C. for 120 minutes. After completion of the heat treatment, the carbon plate was taken out of the heat treatment unit and moved to the acid feeding unit, and 0.2 mL each of 20% by mass hydrofluoric acid and 20% by mass nitric acid was added. Subsequently, the carbon plate was moved to an ozone gas treatment unit, and treated at 50 ° C. for 30 minutes while flowing 10 mL of ozone gas per minute. Subsequently, the carbon plate was moved to a heat treatment unit and subjected to heat treatment at 120 ° C. for 90 minutes to evaporate and remove the silicon content. Next, the carbon plate was moved again to the acid feeding unit, and 1 mL of 2 mass% nitric acid was added to prepare a sample for elemental analysis. Finally, the carbon plate was moved to the element analysis sample feeding unit, and the prepared element analysis sample was automatically injected into the element analysis device to analyze the impurity elements. The results are shown in Table 1.

[Example 2]
In the same manner as in Example 1, 0.5 mL of tetraethoxysilane was injected into a 5 mL sample container made of a fluorocarbon resin set on a carbon plate.
The following operations were programmed in advance and operated automatically. First, with the robot arm, the sample container was moved to the acid feeding unit while being mounted on the carbon plate, and 0.2 mL each of 20% by mass hydrofluoric acid and 20% by mass nitric acid was added. Subsequently, the carbon plate was moved to a heat treatment unit and heat treated at 130 ° C. for 20 minutes. Next, the carbon plate was again moved to the acid feeding unit, and 0.2 mL each of 20% by mass hydrofluoric acid and 20% by mass nitric acid was added. Next, the carbon plate was moved again to the heat treatment unit and heat treated at 180 ° C. for 4 hours to evaporate and remove the silicon component. Next, the carbon plate was moved again to the acid feeding unit, and 1 mL of 2 mass% nitric acid was added to prepare a sample for elemental analysis. Finally, the carbon plate was moved to the element analysis sample feeding unit, and the prepared element analysis sample was automatically injected into the element analysis device to analyze the impurity elements. The results are shown in Table 1.

[Comparative Example 1]
A sample for elemental analysis was prepared by diluting 0.5 mL of the PGEE solution containing 10% by mass of polysiloxane used in Example 1 500 times with clean PGEE. This elemental analysis sample was injected into an elemental analyzer (7700s manufactured by Agilent Technologies) to analyze the impurity elements. The results are shown in Table 2.

[Comparative Example 2]
A sample for elemental analysis was prepared by diluting 0.5 mL of tetraethoxysilane used in Example 2 500 times with clean PGEE. This elemental analysis sample was injected into an elemental analyzer (7700s manufactured by Agilent Technologies) to analyze the impurity elements. The results are shown in Table 2.

  As shown in Tables 1 and 2, in Comparative Examples 1 and 2 in which elemental analysis was performed by diluting the sample 500 times without decomposing the silicon-containing compound in the sample and removing the silicon content, Example 1 in which an impurity element having a concentration of 0.5 ppb or less could not be detected, but a pretreatment for decomposing the silicon-containing compound in the sample to remove silicon was performed, and elemental analysis was performed without dilution. 2 was able to detect an impurity element having a concentration of up to 0.5 ppt, which is 1,000 times the accuracy of the comparative example.

  From the above, according to the elemental analysis method of the present invention, by removing the silicon content in the sample, the impurity element, which could be measured only with an accuracy of 0.5 ppb in the past, is 1,000 times as accurate as the conventional method. It became clear that it can measure with the accuracy of 0.5ppt. In addition, this makes it possible to determine the superiority or inferiority of the technology when developing a technology aimed at improving performance by removing impurity elements in the silicon-containing resist underlayer film forming material and the interlayer insulating film forming material. As a result, it becomes possible to improve the performance of the above-described material and a semiconductor device manufactured using the material.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

1 ... automatic gas phase decomposition apparatus, 2 ... robot arm, 3 ... carbon plate,
4 ... Sample container, 5 ... Acid feed unit, 6 ... Ozone gas treatment unit,
7 ... Heat treatment unit, 8 ... Sample injection port,
9 ... Sample feeding unit for elemental analysis.

Claims (14)

A method for analyzing impurity elements in a sample containing a silicon-containing compound,
Using an automatic vapor phase decomposition apparatus equipped with at least a heating mechanism, a liquid feeding mechanism, and a conveyance mechanism, the silicon-containing compound contained in the sample is decomposed, and the silicon content in the sample after the decomposition is removed. An elemental analysis method comprising preparing an elemental analysis sample, automatically injecting the prepared elemental analysis sample into an elemental analysis apparatus, and analyzing an impurity element in the elemental analysis sample. In the automatic gas phase decomposition apparatus,
(1) A step of adding any one of nitric acid and hydrofluoric acid or a mixture thereof to the sample,
(2) a step of decomposing the silicon-containing compound in the sample by either or both of ozone gas treatment and heat treatment;
(3) heat-treating the sample after decomposition, evaporating and removing the silicon content in the sample after decomposition, and (4) dissolving the sample from which the silicon content has been removed in an acid,
The elemental analysis method according to claim 1, wherein the elemental analysis sample is prepared by automatically performing the step.   The elemental analysis method according to claim 2, wherein the sample is concentrated or evaporated to dryness by heat treatment at 30 ° C. or more and 300 ° C. or less before the step (1).   The elemental analysis method according to claim 2 or 3, wherein nitric acid, hydrofluoric acid, or a mixture thereof is added before and after any of the steps (1) to (4).   The elemental analysis method according to any one of claims 2 to 4, wherein the heat treatment in the step (2) is performed at 30 ° C or higher and 300 ° C or lower.   The elemental analysis method according to any one of claims 2 to 5, wherein the heat treatment in the step (3) is performed at 35 ° C or higher and 350 ° C or lower.   7. The elemental analysis method according to claim 2, wherein the acid used in the step (4) is any one of nitric acid and hydrofluoric acid, or a mixture thereof.   The element analysis method according to claim 1, wherein the sample is a coating material for forming a silicon-containing film used in a semiconductor device manufacturing process.   The element analysis method according to any one of claims 1 to 8, wherein the sample includes a silane monomer.   The elemental analysis method according to any one of claims 1 to 9, wherein the sample includes a polymer compound containing a silicon atom in a repeating unit.   The elemental analysis method according to claim 10, wherein the polymer compound containing a silicon atom in the repeating unit is a polysiloxane compound.   The elemental analysis method according to any one of claims 1 to 11, wherein the sample is an aqueous solution or an organic solvent solution of the silicon-containing compound.   The element according to any one of claims 1 to 12, wherein the elemental analyzer is any one of an inductively coupled plasma mass spectrometer, an inductively coupled plasma emission spectrometer, and an atomic absorption spectrometer. Analysis method.   The elemental analysis method according to any one of claims 1 to 13, wherein the automatic gas phase decomposition apparatus includes an ozone gas treatment unit.

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