JP6400475B2 - Component analysis apparatus and component analysis method - Google Patents

Description

  The present invention relates to an apparatus and method for analyzing a component contained in a solid target, and more specifically to an apparatus and method for analyzing a component that can satisfactorily prepare an analysis sample liquid. It is.

  Inductively coupled plasma mass spectrometry (ICP-MS), which is known as an example of elemental analysis, is a mass spectrometry using argon plasma as an ionization source, and has a high detection sensitivity with a detection limit of ppt level. Rapid simultaneous quantification of about 60 elements is possible. In addition to ICP-MS, inductively coupled plasma atomic emission spectrometry (ICP-AES), atomic absorption spectrometry (AAS), and the like can be given as elemental analysis methods. Such elemental analysis methods are used for analyzing components in a wide range of fields such as semiconductors, electrical machinery, steel and non-ferrous metals, chemistry, food, and the environment.

  By the way, in recent years, silicon carbide has attracted attention as a ceramic material and its application has been promoted. Since such a ceramic material is required to have high purity, development of an accurate analysis method of impurities and an apparatus for the same are also being developed.

  As a method for analyzing components contained in silicon carbide, the chemical analysis method for silicon carbide fine powder described in Non-Patent Document 1 is known. According to the method described in Non-Patent Document 1, silicon carbide is immersed in a mixed acid solution in which a plurality of acids are mixed, heated and pressurized, and silicon carbide is dissolved in the mixed acid solution to obtain an analysis sample solution. A metal component contained in the analysis sample is detected.

JIS R 1616 "Method for chemical analysis of fine powder of silicon carbide for fine ceramics"

  Non-Patent Document 1 is a method in which a powdered silicon carbide sample is immersed in a mixed acid as it is to dissolve the whole. Therefore, for example, the sample is a molded product, and only a specific region of the surface cannot be an analysis target. In the field of ceramic materials or the like, there are cases where it is only necessary to set the material surface or the surface layer as an analysis target instead of the entire material, but in the method of Non-Patent Document 1, only such a specific region is to be inspected. It can not be.

  The present invention has been tried in view of the above problems, and its purpose is to be able to prepare an analysis sample solution in a short time, to have quantitative properties, and to analyze only a specific region. It is to provide a component analysis apparatus and method.

Therefore, in order to solve the above problems, the component analysis apparatus according to the present invention,
A component analyzer for analyzing a component of a solid target,
Laser irradiation means for irradiating laser light to at least one location on the surface of the solid target, and generating fine particles of the solid target from the at least one location;
Supporting means for supporting the solid target;
With
The support means is made of a material that transmits the laser light emitted from the laser irradiation means and does not elute the analysis target component.
The component analyzer is
A capture region that captures the fine particles, and forms a capture region that is in contact with the surface of the solid target supported by the support means; and
Liquid supply means for supplying a liquid to the inside of the capture region forming section;
Further comprising
The fine particles are collected in the liquid, and component analysis of the fine particles is performed.

In addition, the component analysis method according to the present invention, in order to solve the above problems,
A component analysis method for analyzing a component of a solid target, which is performed using the above-described component analyzer,
A laser irradiation step of irradiating laser light to at least one location on the surface of the solid target to generate fine particles of the solid target from the at least one location;
Including a liquid supply step for supplying a liquid into the capture region forming part,
The fine particles are collected in the liquid, and component analysis of the fine particles is performed.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the component analysis apparatus and method which have quantitative property and can make only a specific area | region analysis object.

It is a block diagram which shows the structure of the impurity analyzer which is one form of the component analyzer of this invention. It is a figure which shows the structure of the dispersion liquid preparation part of the impurity analyzer shown in FIG. It is a block diagram which shows the structure of the modification of the impurity analyzer shown in FIG. It is a block diagram which shows the structure of the modification of the impurity analyzer shown in FIG. It is a block diagram which shows the structure of the modification of the impurity analyzer shown in FIG. It is a figure which shows the structure of the modification of the dispersion preparation part of the impurity analyzer shown in FIG. It is a figure which shows the structure of the modification of the dispersion preparation part of the impurity analyzer shown in FIG. FIG. 3 is a graph showing the results of Example 1. FIG. 6 is a graph showing the results of Example 2.

  The inventors of the present application, for example, have a disadvantage that a known analysis method including the above-mentioned Non-Patent Document 1 requires a relatively long time, and that only a specific region of a solid target cannot be analyzed. In view of the above, the present inventors have found that there is room for improvement in a process for preparing a sample to be subjected to an analysis process such as inductively coupled plasma mass spectrometry (ICP-MS), and the present invention has been completed. As described above, it is known that a sample to be subjected to an analysis step is prepared by decomposing a solid target using a mixed acid solution in which a plurality of acids are mixed. Therefore, the inventors of the present application have found that the solid target fine particles are generated from a specific region of the solid target, and the fine particles are used as a sample for component analysis, and the present invention has been completed.

  Hereinafter, an embodiment of a component analysis apparatus and a component analysis method according to the present invention will be described.

  One form of the component analyzer according to the present invention is an impurity analyzer for analyzing impurities contained in a solid target. Here, as the solid target, a well-known impurity analysis object can be mentioned. The most suitable as the solid target is ceramic such as alumina, zirconia, silicon carbide, etc. A compound semiconductor is more suitable next, and an organic compound such as a fluororesin and a chlorinated polyether is more suitable next. Examples of the impurity include at least one atom or molecule of metal, nonmetal, and ion.

  In the following embodiment, a ceramic material is cited as a solid target, and an aspect of analyzing whether or not a metal impurity is contained in the ceramic material will be described. Note that the present invention is not limited to this.

  FIG. 1 is a block diagram showing a main configuration of an impurity analyzer 10 (component analyzer) in the present embodiment. The impurity analyzer 10 in this embodiment includes a dispersion creating unit 1 (laser irradiation unit), a decomposition unit 2 (decomposition unit), and an analysis unit 3 (analysis unit).

  In the dispersion creating unit 1, a part of the ceramic material is sectioned in the liquid (in the trapping region) to generate fine particles, and a dispersion in which the fine particles are dispersed in the liquid is created. Hereinafter, the dispersion liquid preparation part 1 is explained in full detail using FIG.

  FIG. 2 is a diagram showing a configuration of the dispersion creating unit 1. The dispersion preparation unit 1 includes a stage 12 (support means), a bottom plate 13 (support means) disposed on the stage 12, a cover plate 16 (cover means) disposed opposite to the bottom plate 13, the bottom plate 13 and the cover plate 16. The side wall 14 which is arrange | positioned between these and supports the cover plate 16, and the laser irradiation apparatus 17 are provided. In addition, a liquid supply means (not shown) is provided in a sealed space surrounded by the bottom plate 13, the lid plate 16 and the side wall 14, specifically, in a concave container (capture region forming portion) formed by the bottom plate 13 and the side wall 14. The liquid 15 (capture region) supplied from is stored, and the ceramic material 50 is allowed to stand on the bottom plate 13 while being immersed in the liquid 15.

  The dispersion creating unit 1 irradiates the ceramic material 50 immersed in the liquid 15 placed on the bottom plate 13 with a laser beam 70 and causes laser ablation on the ceramic material 50 in the irradiated region to generate fine particles. To do. The generated fine particles are released into the liquid 15 and dispersed.

  Laser light 70 emitted from the laser irradiation device 17 passes through the cover plate 16 as shown in FIG. 2 and is irradiated onto the ceramic material 50 in the liquid 15. Specifically, the laser beam 70 is applied to at least one of the regions of the ceramic material 50 facing the cover plate 16. Then, the surface of the solid target within the irradiation range is irradiated with the laser beam 70 and becomes a slice. These slices are fine particles, and the fine particles are released into the liquid 15 (laser irradiation step).

  The laser beam 70 emitted from the laser irradiation device 17 can be appropriately selected from the following conditions.

  For example, the pulse width is preferably selected from the range of 100 femtoseconds to 100 nanoseconds. This is because if the pulse width exceeds 100 nanoseconds, particles may not be efficiently generated and collected. The pulse width is further preferably selected from the range of 100 picoseconds to 100 nanoseconds, and more preferably selected from 1 nanosecond to 100 nanoseconds.

  The wavelength is preferably selected from the range of 10 nm to 10.6 μm. This is because if the thickness is less than 10 nm or exceeds 10.6 μm, the ceramic material may not generate particles efficiently. The wavelength is further preferably selected from the range of 193 nm to 10.6 μm, and more preferably selected from 213 nm to 10.6 μm.

  As a laser light source provided in the laser irradiation device 17, a YAG laser, an excimer laser, a nitrogen laser, an Ar ion laser, a dye laser, a semiconductor laser, a titanium sapphire laser, a glass laser, or the like is used.

  By irradiating the ceramic material 50 with the laser light 70 having such various conditions, fine particles can be generated from a fine region (0.1 to 10 μm from the surface layer) of the ceramic material 50, and impurities in this fine region Analysis can be performed with high accuracy. The fine region is not limited to the range of 0.1 to 10 μm from the surface layer. For example, by repeatedly irradiating the same portion with the laser beam 70, fine particles can be generated from a region deeper than 10 μm from the surface layer, and the fine particles can be subjected to impurity analysis.

  In FIG. 2, the laser irradiation device 17 is above the installation position of the ceramic material 50, and the laser light is emitted downward and irradiated on the upper surface of the ceramic material 50 located below. ing. However, the present invention is not limited to the positional relationship shown in FIG. 2 with respect to the positional relationship between the laser irradiation device and the ceramic material as long as the laser beam is irradiated onto the region in contact with the liquid 15 in the ceramic material. Absent. For example, a mode in which laser light enters the liquid 15 from the side and irradiates the side surface of the ceramic material 50 shown in FIG. Moreover, the aspect which irradiates the ceramic material 50 by changing an optical path in the middle using the reflecting mirror etc. in the light emitted from the laser irradiation apparatus may be sufficient.

  In addition, when the irradiation diameter (light diameter) of the laser beam 70 of the ceramic material 50 is smaller than the desired irradiation area, the irradiation range is widened by moving the laser irradiation apparatus using a moving means (not shown). The desired irradiation region can be irradiated with laser light.

  The cover plate 16 is configured to be in close contact with the upper end portion of the side wall 14 so that dust or dust does not enter the liquid 15 from the laser irradiation device 17 side. The lid plate 16 is made of a material that allows the laser light 70 to pass through without being scattered. Specifically, it can be made of quartz, but the present invention is not limited to this.

  The bottom plate 13 is also preferably made of a material that is not scraped when the absorption rate of the laser light 70 is poor. A specific example of this is quartz.

The lid plate 16 and the bottom plate 13 may be other than quartz, and specific examples thereof include CaF ₂ (calcium fluoride), BaF ₂ (barium fluoride), ZnSe (zinc selenide), MgF ₂ (fluorine). Magnesium fluoride), KRS-5 (thallium bromoiodide), LiF (lithium fluoride), and the like. By selecting from these materials including quartz, it is possible to avoid damage caused by laser light and to avoid the components of the cover plate 16 and the bottom plate 13 from being mixed in the liquid, thereby realizing accurate analysis. Can do.

  The side wall 14 is preferably made of a material that is resistant to the liquid 15 and that does not elute the analysis target component, that is, a contamination-free material.

  Here, the liquid 15 is not adversely affected because the ceramic material 50 is decomposed in the decomposition unit 2 that performs a later process, and is also adversely affected because impurities are analyzed in the analysis unit 3 that performs a later process. There is no particular limitation if a liquid that does not become used is used. As the liquid 15, for example, an organic solvent or ultrapure water can be used. Among these, if ultrapure water is used as the liquid 15, it is preferable because processing in the decomposition unit 2 that is a subsequent process can be performed smoothly. This point will be described later. In the present embodiment, the ceramic material is a solid target. However, the present invention does not limit the analysis target to a ceramic material, and therefore the liquid 15 may be appropriately selected according to the solid target to be analyzed.

  In the present embodiment, fine particles of the ceramic material 50 are created by causing laser ablation in the dispersion creating unit 1 as described above. Therefore, the dispersion creating unit 1 is not intended to decompose the ceramic material 50 with the liquid 15.

  That is, in the present specification, “dispersion” means a state in which a part of the solid target (ceramic material 50) is released as fine particles into the liquid 15, and the solid target and the fine particles do not react with the liquid 15, Therefore, in the decomposition part 2, the solid target and the fine particles do not react with the liquid and the physical properties and composition do not change. On the other hand, “decomposition” in the specification of the present application refers to a phenomenon that occurs in the decomposition unit 2 described later, and fine particles react with the decomposition solution in the decomposition solution (of the decomposition unit 2) to become ions, atoms, or molecules. Represents a phenomenon. Note that “decomposition” can be restated as dissolution.

  As described above, the dispersion creating unit 1 is not intended to decompose the ceramic material 50 and the fine particles with the liquid 15 but to create a dispersion only. In this embodiment, it is possible to analyze the impurities only in the specific region by generating the fine particles from a specific region of the ceramic material 50 and decomposing the fine particles in a later process. Because it becomes. However, in the case where analysis of only a specific region is not required, the present invention is not limited to this, and in the dispersion liquid creating unit 1, the ceramic material 50 and the fine particles react with the liquid 15 and decompose as the fine particles are generated. It is good also as an aspect which progresses. In the case where the dispersion preparation unit 1 proceeds with decomposition along with the generation of the fine particles, among the acid solutions used in the decomposition unit 2 to be described later, an acid solution that does not interfere with the generation of fine particles by laser ablation is used as the liquid 15. That's fine.

In the present embodiment, a mode in which the fine particles generated in the dispersion liquid preparation unit 1 are decomposed and used for impurity analysis will be described. It is also possible to directly analyze the fine particles generated in the dispersion preparation unit 1 without performing the decomposition in the decomposition unit 2 described later. That is, in the component analyzer (component analysis method) according to the present invention, the decomposition unit 2 (decomposition step) described later is not essential. However, when the particle diameter of the fine particles generated in the dispersion creating unit 1 exceeds 1 nm, decomposition by the decomposition unit 2 is preferable, and when exceeding 1 μm, decomposition by the decomposition unit 2 is necessary. Even when the particle diameter exceeds 1 nm and is 1 μm or less, it may be preferable to perform decomposition by the decomposition unit 2 because it may lack quantitativeness. In addition, the aspect which does not require the decomposition | disassembly part 2 (decomposition | disassembly process) is demonstrated in a later modification.

  The decomposition unit 2 decomposes the fine particles dispersed in the dispersion prepared in the dispersion preparation unit 1 (decomposition step).

  In the present embodiment, the decomposition unit 2 first collects fine particles from the dispersion created by the dispersion creation unit 1. Examples of the recovery method include a method of removing the liquid 15 (medium) by heating and drying a dispersion liquid (a liquid in which fine particles are dispersed), but is not limited thereto. This recovery process may be performed in the dispersion preparation unit 1 in the previous step.

  The collected microparticles are then (i) an acid comprising at least one acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, nitric acid, perchloric acid, sulfuric acid, acetic acid, formic acid, hydrogen peroxide and phosphoric acid. Solution, (ii) alkaline solution such as sodium hydroxide solution, calcium hydroxide solution or ammonia solution, or (iii) solution of organic solvent such as hexane, benzene, toluene, chloroform, acetone, ethanol, methanol, isopropyl alcohol, etc. Contact with. Thereby, the fine particles are decomposed.

  In the decomposition unit 2, a certain container is prepared, and the fine particles and the acid solution, the alkaline solution, or the organic solvent are accommodated therein, so that the fine particles and the acid solution, the alkaline solution, or the organic solvent are brought into contact with each other. . The configuration of the decomposition unit 2 can be realized by sharing at least a part of the configuration of the dispersion creating unit 1. However, the present invention is not limited to this, and the dispersion preparation unit 1 and the decomposition unit 2 may be configured separately. That is, after recovering the dispersion liquid from the dispersion liquid creating section 1, the recovered liquid may be transferred to the decomposition section 2 having another configuration to evaporate the liquid 15 (medium). Here, in the case where ultrapure water is used as the liquid 15 as described above in the dispersion creating unit 1, the liquid 15 is not removed from the dispersion after separating the dispersion from the ceramic material 50. The decomposition solution may be prepared by adding an acid solution, an alkali solution, or an organic solvent to ultrapure water.

  Due to the decomposition in the decomposition unit 2, ceramic atoms or ionized products derived from the fine particles (fine particles of the ceramic material) and impurities are included as decomposed products. That is, a liquid containing ceramic atoms or ionized substances and impurities is used as an analysis sample for impurity analysis by the analysis unit 3 in a later process.

  In the separation unit 2, the liquid in which the fine particles are brought into contact with the acid solution, the alkali solution, or the organic solvent may be heated and / or pressurized.

  The analysis unit 3 performs impurity analysis using the analysis sample created by the above-described method. As the analysis method, a conventionally known method can be adopted. Specifically, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), atomic absorption spectrometry (AAS), capillary electrophoresis, or ion chromatography was used. Impurity analysis can be employed.

  The analysis sample created by the decomposition unit 2 may be subjected to analysis by the analysis unit 3 after adjusting the medium as appropriate.

  According to the present embodiment, laser ablation is performed by irradiating a specific portion of the ceramic material 50 with laser light, and an analysis sample to be used for impurity analysis is prepared using the obtained fine particles decomposed. . As a result, compared to the conventional configuration in which the solid target (ceramic material 50) as it is is subjected to decomposition treatment, the decomposition efficiency can be improved because it is fine particles, and the preparation time for preparing a sample for impurity analysis is shortened. can do.

  The fine particles are generated from a specific portion of the ceramic material 50. Therefore, only a specific part of the ceramic material 50 can be an object of impurity analysis.

  Further, in the dispersion liquid creating unit 1, the ceramic material 50 placed in the liquid 15 is laser ablated to disperse the fine particles to be analyzed in the liquid 15, so that the fine particles are obtained by laser ablation in the gas phase. Compared with the case where it produces | generates, the collection | recovery rate of microparticles | fine-particles is high. Therefore, accurate impurity analysis can be realized.

  In the present embodiment, an aspect of performing an impurity analysis of a ceramic material is described. This is because according to the component analysis apparatus and the component analysis method of the present invention, high analysis accuracy can be realized even when analyzing a very small amount of components (= impurities). However, the present invention can be applied not only to impurity analysis but also to component analysis (for example, principal component analysis).

[Modification A]
As described above, the decomposition unit 2 (decomposition step) described in the present embodiment is not an essential configuration in the present invention.

  In this embodiment, although the aspect which decomposes | disassembles the microparticles | fine-particles produced | generated by the dispersion liquid preparation part 1 using an acid solution, an alkaline solution, or an organic solvent was demonstrated, this decomposition process is the fine particle produced | generated by the dispersion liquid preparation part 1. This treatment is necessary when the particle size is fine metal particles of 1 μm or more.

  However, the present invention is not limited to the case where the fine particles generated by the dispersion creating unit 1 are metal, and is not limited to the case where the particle diameter is 1 μm or more. For example, when the metal fine particle is 1 nm or less, the decomposition process by the decomposition unit 2 is not necessary, and the fine particle (1 nm or less) generated by the dispersion creating unit 1 is directly analyzed by the analysis unit 3 as it is. It is possible. As described above, the method for preparing the sample subjected to the analysis in the analysis unit 3 varies depending on the particle size of the fine particles generated in the dispersion creating unit 1.

  Below, the aspect which does not require the decomposition | disassembly by the decomposition | disassembly part 2 is given, giving three examples as modification A (1) -A (3).

-Modification A (1)
FIG. 3 is a block diagram showing a main configuration of the impurity analyzer (component analyzer) of Modification A (1).

  The impurity analyzer 10 of the present modified example A (1) realizes an aspect in which the analysis unit 3 directly analyzes the fine particles generated by the dispersion preparation unit 1 described above.

  This aspect can be applied when the particle diameter of the fine particles generated by the dispersion creating unit 1 is 1 nm or less. In order to generate fine particles having a particle diameter of 1 nm or less in the dispersion liquid creating unit 1, the laser irradiation conditions of the laser irradiation apparatus may be set as appropriate.

-Modification A (2)
FIG. 4 is a block diagram showing a main configuration of the impurity analyzer (component analyzer) of Modification A (2).

  The impurity analyzer 10 of the present modification A (2) includes a sample adjustment unit 22 instead of the decomposition unit 2 of the above-described embodiment. And the impurity analyzer 10 of this modification A (2) makes the sample preparation part 22 centrifuge the dispersion liquid produced in the dispersion liquid preparation part 1 mentioned above. And the aspect which analyzes the supernatant in the analysis part 3 is implement | achieved.

  In the case of the modification A (2), it is assumed that when the fine particles produced in the dispersion liquid producing unit 1 are measured as they are in the analyzing unit 3, the fine particles themselves enter the analyzing unit 3 and a correct analysis cannot be performed. Can be applied to.

-Modification A (3)
FIG. 5 is a block diagram showing a main configuration of an impurity analyzer (component analyzer) according to Modification A (3).

  The impurity analyzer 10 of the present modification A (3) includes an extraction unit 22 ′ instead of the decomposition unit 2 of the above-described embodiment. And the impurity analyzer 10 of this modification A (3) is the aspect which extracts the component for analysis from the microparticles | fine-particles created by the dispersion preparation part 1 in the extraction part 22 ', and analyzes an impurity in the analysis part 3 Is realized.

  Specifically, the extraction unit 22 'extracts components for analysis by heating, contact with a solvent that does not dissolve fine particles (acid solution, alkali solution, or organic solvent), ultrasonic application, or stirring operation. To do.

[Modification B]
As shown in FIG. 2, the dispersion creating unit 1 described in the above embodiment stores the liquid 15 in a sealed space surrounded by the bottom plate 13, the cover plate 16, and the side wall 14 using a liquid supply unit (not shown). Although the laser irradiation is performed on the ceramic material 50 immersed in the liquid 15, the present invention is not limited to this. For example, there can be the following modified examples B (1) and B (2).

-Modification B (1)
FIG. 6 is a view showing a modified example, and is a drawing corresponding to FIG. 2. However, as shown in FIG. 6, even if there is no cover plate 16 of FIG. It is possible to collect the fine particles in the liquid 15 by storing the liquid 15 inside the container and capturing the fine particles generated by the laser irradiation in the liquid 15.

-Modification B (2)
FIG. 7 shows another modification. FIG. 7 shows a configuration in which the liquid 15 in FIG. 2 does not exist in the sealed space (capture region) surrounded by the bottom plate 13, the cover plate 16, and the side wall 14. That is, the bottom plate 13, the cover plate 16, and the side wall 14 are capture region forming portions that form a supplemental region. The configuration of FIG. 7 irradiates the laser in a sealed space (cell) with no liquid. In the case of this configuration, for example, liquid can be supplied into the cell after laser irradiation from a liquid supply unit (not shown) provided on the side wall 14, and the generated fine particles can be collected in the liquid. The aspect can also be realized as a modification of the dispersion creating unit 1 of the embodiment.

[Summary]
The component analyzer according to the present invention is as described above.
A component analyzer for analyzing a component of a solid target,
Laser irradiation means for irradiating laser light to at least one location on the surface of the solid target, and generating fine particles of the solid target from the at least one location;
Supporting means for supporting the solid target;
With
The support means is made of a material that transmits the laser light emitted from the laser irradiation means and does not elute the analysis target component.
The component analyzer is
A capture region that captures the fine particles, and forms a capture region that is in contact with the surface of the solid target supported by the support means; and
Liquid supply means for supplying a liquid to the inside of the capture region forming section;
Further comprising
The fine particles are collected in the liquid, and component analysis of the fine particles is performed.

  According to the above configuration, compared to the conventional configuration in which the solid target is subjected to the decomposition process, laser ablation is performed by irradiating a specific portion of the solid target with laser light, and the obtained fine particles are decomposed to analyze the components. Therefore, the decomposition efficiency can be improved, and the preparation time for preparing the sample for component analysis can be shortened.

  Moreover, according to said structure, since it can measure after decomposing | disassembling a solid target in a solution and preparing a sample, compared with the laser ablation ICP-MS method which measures a solid target directly, quantitative property is good. High measurement can be realized.

  The fine particles are generated from a specific part of the solid target. Therefore, only a specific part of the solid target can be the target of component analysis.

  Further, since the support means is made of a material that transmits laser light and does not elute the analysis target component (for example, quartz), the support means is not scraped by the laser light. The component derived from is not mixed in the liquid. Therefore, highly accurate component analysis becomes possible.

In addition to the above configuration, the component analyzer according to the present invention includes:
The capture region forming unit may have a cover unit made of a material that transmits laser light emitted from the laser irradiation unit and does not elute the analysis target component between the laser irradiation unit and the solid target. .

  According to the above configuration, the capture region forming portion has the cover means made of a material that transmits laser light and does not elute the analysis target component (for example, quartz). Since the means is not shaved, components derived from the material of the cover means are not mixed into the capture region during laser irradiation.

In addition to the above configuration, the component analyzer according to the present invention includes:
The capture region is constituted by the liquid supplied from the liquid supply means into the capture region forming unit,
The laser irradiation means generates the fine particles by irradiating laser light to at least one place on the surface of the solid target in contact with the liquid,
It is possible to adopt a configuration in which the fine particles are collected in the liquid by being captured by the liquid.

  According to the above configuration, the laser beam is produced in the gas phase because the solid target is laser ablated at the location where the liquid is in contact and the fine particles to be analyzed are dispersed in the liquid. Compared with the case where fine particles are produced by ablation, the recovery rate of fine particles is high. Therefore, accurate component analysis can be realized.

In addition to the above configuration, the component analyzer according to the present invention includes:
The capture region is constituted by a sealed space containing the solid target inside,
The component analyzer may be configured such that the fine particles generated in the sealed space are recovered by the liquid supplied after the fine particles are generated in the sealed space.

In addition to the above configuration, the component analyzer according to the present invention includes:
The laser irradiation means can irradiate only a part of the surface of the solid target with laser light to generate the fine particles from the part of the area.

In addition to the above configuration, the component analyzer according to the present invention includes:
It is possible to further comprise analysis means for performing component analysis of the fine particles by performing component analysis of a dispersion liquid collected in the liquid and in which the fine particles are dispersed in the liquid.

In addition to the above configuration, the component analyzer according to the present invention includes:
It is possible to further include a decomposing means for decomposing the fine particles using an acid solution, an alkali solution, or an organic solvent to obtain a component analysis sample.

In addition to the above configuration, the component analyzer according to the present invention includes:
The above component analysis is performed using inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), atomic absorption spectrometry (AAS), capillary electrophoresis, or ion chromatography. It is possible to do this.

In addition to the above configuration, the component analyzer according to the present invention includes:
As the liquid, it is possible to use a liquid that does not dissolve the solid target.

  According to the above configuration, neither the solid target nor the fine particles are decomposed by the liquid at the stage of generating the fine particles from the solid target. Therefore, if the component analysis is performed on only the fine particles later, the components of the fine particles can be accurately analyzed.

  This means that the component analysis of a specific region of the solid target can be accurately performed.

In addition to the above configuration, the component analyzer according to the present invention includes:
Ultrapure water can be used as the liquid.

  According to said structure, by using ultrapure water as said liquid, it does not react with a solid target, Therefore It becomes possible to make only a microparticle into the object of component analysis.

In addition to the above configuration, the component analyzer according to the present invention includes:
It is possible to analyze the impurity component of the fine particles contained in the dispersion obtained by dispersing the fine particles in the liquid in contact with the at least one location.

The component analysis method according to the present invention is as described above.
A component analysis method for analyzing a component of a solid target, which is performed using the above-described component analyzer,
A laser irradiation step of irradiating laser light to at least one location on the surface of the solid target to generate fine particles of the solid target from the at least one location;
Including a liquid supply step for supplying a liquid into the capture region forming part,
The fine particles are collected in the liquid, and component analysis of the fine particles is performed.

  According to the above configuration, compared to the conventional configuration in which the solid target is subjected to the decomposition process, laser ablation is performed by irradiating a specific portion of the solid target with laser light, and the obtained fine particles are decomposed to analyze the components. Therefore, the decomposition efficiency can be improved, and the preparation time for preparing the sample for component analysis can be shortened.

  Moreover, according to said structure, since it can measure after decomposing | disassembling a solid target in a solution and preparing a sample, compared with the laser ablation ICP-MS method which measures a solid target directly, quantitative property is good. High measurement can be realized.

  The fine particles are generated from a specific part of the solid target. Therefore, only a specific part of the solid target can be the target of component analysis.

Further, the component analysis method according to the present invention, in addition to the above configuration,
The liquid supply step supplies the liquid to the inside of the capture region forming unit before the laser irradiation step,
In the laser irradiation step, the fine particles are generated by irradiating laser light to at least one place on the surface of the solid target in contact with the liquid,
It is possible to adopt a configuration in which the fine particles are collected in the liquid by being captured by the liquid.

  According to the above configuration, the laser beam is produced in the gas phase because the solid target is laser ablated at the location where the liquid is in contact and the fine particles to be analyzed are dispersed in the liquid. Compared with the case where fine particles are produced by ablation, the recovery rate of fine particles is high. Therefore, accurate component analysis can be realized.

Further, the component analysis method according to the present invention, in addition to the above configuration,
Among the component analyzers having the above-described configuration, a cover unit made of a material that transmits laser light emitted from the laser irradiation unit and does not elute the analysis target component between the laser irradiation unit and the solid target. The closed space formed by the support means and the cover means is configured as the capturing region, and the solid target is held in the sealed space, and is captured in the sealed space. In the component analysis apparatus configured to recover the fine particles generated from the at least one place in the form of a dispersion in which the fine particles are dispersed in the liquid and perform component analysis of the fine particles.
The capture region is constituted by a sealed space containing the solid target inside,
In the laser irradiation step, at least one part of the surface of the solid target that is in contact with the sealed space is irradiated with laser light to generate the fine particles,
The liquid supply step may be configured to supply the liquid to the sealed space after the fine particles are generated.

Further, the component analysis method according to the present invention, in addition to the above configuration,
In the laser irradiation step, it is possible to irradiate only a partial region of the surface of the solid target with a laser beam and generate the fine particles from the partial region.

Further, the component analysis method according to the present invention, in addition to the above configuration,
It is possible to further include a decomposition step in which the fine particles are decomposed using an acid solution, an alkaline solution, or an organic solvent to obtain the sample.

Further, the component analysis method according to the present invention, in addition to the above configuration,
Using the above sample, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), atomic absorption spectrometry (AAS), capillary electrophoresis, or ion chromatography It is possible to further include an analysis step for performing the used component analysis.

[Example 1]
-About collection efficiency It will be as follows if one Example of the component analyzer which concerns on this invention and a component analysis method is demonstrated.

Using a Si substrate and a SiC substrate as the ceramic material 50 shown in FIG. 1, ablated particles were generated in the liquid (ultra pure water) using a solution laser ablation method for each substrate. The laser irradiation conditions are a YAG laser with a wavelength of 213 nm and an output of 4 GW / cm ² . Further, the irradiation area was a 5 mm square area (Si substrate) and a 1 mm square area (SiC substrate).

  After the produced ablated particles were collected by a syringe, the collected liquid was acid-decomposed (specifically, nitric acid and hydrofluoric acid were added), and then the silicon (Si) concentration was measured by ICP-MS.

  The collection efficiency of the ablated particles into the solution was calculated by comparing the amount of Si contained in the solution from which the particles were collected with the amount of Si calculated from the volume of the ablation trace.

  As a result, it was confirmed that all particles ablated on both the Si substrate and the SiC substrate were recovered in the solution (FIG. 8).

[Example 2]
-About recovery rate of trace metal elements In this Example 2, the glass standard substance was pretreated in the same manner as in Example 1, and trace metal elements were measured by ICP-MS. And the recovery rate of the trace metal element was calculated | required by comparing a reference material certification | authentication value and a measured value.

  As a result, good recoveries were obtained for all the elements (FIG. 9).

Example 3
In Example 1, a dispersion was prepared based on the configuration of the dispersion preparation unit 1 in FIG. 2, but an example using the dispersion preparation unit 1 in FIG.

In Example 3, ablation particles were generated in a liquid (ultra pure water) using a solution laser ablation method using a SiC substrate as the ceramic material 50. The laser irradiation conditions are a YAG laser with a wavelength of 213 nm and an output of 4 GW / cm ² . The irradiation area was a 1 mm square area (SiC substrate).

  The produced ablated particles were collected by a syringe under the same conditions as in Example 1, and the collected solution was acid-decomposed, and then the silicon (Si) concentration was measured by ICP-MS.

  As a result, the same result as that obtained using the SiC substrate of FIG. 8 was obtained. That is, even in the dispersion liquid preparation unit 1 in FIG. 6, it was confirmed that all the ablated particles were recovered in the liquid 15.

Example 4
In Example 1, a dispersion was prepared based on the configuration of the dispersion preparation unit 1 in FIG. 2, but the fine particles generated in the sealed space were recovered with ultrapure water even in the dispersion preparation unit 1 in FIG. It was found that it was possible (data not shown).

  It should be noted that the present invention is not limited to each embodiment, modification, and example, and various modifications are possible within the scope of the claims, and are disclosed in each embodiment, modification, and example. Embodiments obtained by appropriately combining the technical means provided are also included in the technical scope of the present invention.

  The present invention can analyze (inspect) impurities contained in an object within a specific range, and therefore can be suitably used particularly for impurity analysis in the semiconductor field.

1 Dispersion preparation unit (liquid contact means, laser irradiation means)
2 Disassembly part (disassembly means)
3 analysis department (analysis means)
10 Impurity analyzer (component analyzer)
12 stages (support means)
13 Bottom plate (supporting means) (capturing area forming part)
14 Side wall (capturing area forming part)
15 Liquid (capture area)
16 Cover plate (cover means)
17 Laser irradiation apparatus 22 Sample adjustment part 22 'Extraction part 50 Ceramic material (solid target)
70 Laser light

Claims (17)

A component analyzer for analyzing a component of a solid target,
Laser irradiation means for irradiating laser light to at least one location on the surface of the solid target, and generating fine particles of the solid target from the at least one location;
Supporting means for supporting the solid target;
With
The support means is made of a material that transmits the laser light emitted from the laser irradiation means and does not elute the analysis target component.
The component analyzer is
A capture region that captures the fine particles, and forms a capture region that is in contact with the surface of the solid target supported by the support means; and
Liquid supply means for supplying a liquid that does not dissolve the solid target into the trapping region forming portion;
Further comprising
Collecting the produced fine particles in the liquid;
The component analyzer is
And decomposing means for the upper Symbol fine particles recovered above, the acid solution, and alkali solution or component analysis sample is decomposed with an organic solvent,
Analysis means for performing component analysis of the component analysis sample;
The component analyzer further comprising:   The capture region forming unit includes a cover unit made of a material that transmits the laser light emitted from the laser irradiation unit and does not elute the analysis target component between the laser irradiation unit and the solid target. The component analysis apparatus according to claim 1. The capture region is constituted by the liquid supplied from the liquid supply means into the capture region forming unit,
The laser irradiation means generates the fine particles by irradiating laser light to at least one place on the surface of the solid target in contact with the liquid,
The component analyzer according to claim 1, wherein the fine particles are collected in the liquid when the produced fine particles are captured in the liquid. A component analyzer for analyzing a component of a solid target,
Laser irradiation means for irradiating laser light to at least one location on the surface of the solid target, and generating fine particles of the solid target from the at least one location;
Supporting means for supporting the solid target;
With
The support means is made of a material that transmits the laser light emitted from the laser irradiation means and does not elute the analysis target component.
The component analyzer is
A capture region that captures the fine particles, and forms a capture region that is in contact with the surface of the solid target supported by the support means; and
Liquid supply means for supplying a liquid to the inside of the capture region forming section;
Analysis means for performing component analysis of the fine particles;
Further comprising
The fine particles are collected in the liquid, the component analysis of the fine particles is performed,
The capture region forming unit has a cover unit made of a material that transmits the laser beam emitted from the laser irradiation unit and does not elute the analysis target component between the laser irradiation unit and the solid target. ,
The capture region is constituted by a sealed space containing the solid target inside,
The component analyzer is configured such that the fine particles generated in the sealed space are collected in the liquid supplied after the fine particles are generated in the closed space. .   The said laser irradiation means irradiates only a partial area | region of the said surface of the said solid target with a laser beam, The said microparticles | fine-particles are produced | generated from the said partial area | region. Component analyzer.   5. The component analyzer according to claim 4, further comprising a decomposing unit that decomposes the fine particles with an acid solution, an alkali solution, or an organic solvent to obtain a component analysis sample.   The above component analysis is performed using inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), atomic absorption spectrometry (AAS), capillary electrophoresis, or ion chromatography. The component analysis apparatus according to claim 1, wherein the component analysis apparatus is performed.   The component analyzer according to claim 4, wherein a liquid that does not dissolve the solid target is used as the liquid.   The component analyzer according to claim 1, wherein ultrapure water is used as the liquid.   The component analysis apparatus according to claim 1, wherein an impurity component of the fine particles is analyzed. A component analysis method for analyzing a component of a solid target, which is performed using the component analyzer according to any one of claims 1 to 10 ,
A laser irradiation step of irradiating laser light to at least one location on the surface of the solid target to generate fine particles of the solid target from the at least one location;
A liquid supply step for supplying a liquid that does not dissolve the solid target inside the capture region forming unit,
Collecting the produced fine particles in the liquid;
In the component analysis method,
The The recovered above Symbol microparticles, acid solution, component analysis method characterized by further comprising a decomposition step of the component analysis samples were decomposed using an alkali solution or an organic solvent. The liquid supply step supplies the liquid to the inside of the capture region forming unit before the laser irradiation step,
In the laser irradiation step, the fine particles are generated by irradiating laser light to at least one place on the surface of the solid target in contact with the liquid,
The component analysis method according to claim 11 , wherein the fine particles are collected in the liquid by capturing the produced fine particles in the liquid. A component analysis method for analyzing a component of a solid target, which is performed using the component analyzer according to claim 2,
A laser irradiation step of irradiating laser light to at least one location on the surface of the solid target to generate fine particles of the solid target from the at least one location;
Including a liquid supply step for supplying a liquid into the capture region forming part,
The fine particles are collected in the liquid, the component analysis of the fine particles is performed,
The capture region is constituted by a sealed space containing the solid target inside,
In the laser irradiation step, at least one part of the surface of the solid target that is in contact with the sealed space is irradiated with laser light to generate the fine particles,
In the liquid supply step, the liquid is supplied to the sealed space after the fine particles are generated. In the above laser irradiation process, by irradiating a laser beam only in a partial area of the surface of said solid target, claim 11, characterized in that to produce the fine particles from the part of the region to 13 The component analysis method according to any one of the above. The component analysis method according to claim 13 , further comprising a decomposition step of decomposing the fine particles using an acid solution, an alkali solution, or an organic solvent to obtain a component analysis sample. The above component analysis using inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectroscopy (ICP-AES), atomic absorption spectrometry (AAS), capillary electrophoresis, or ion chromatography component analysis method according to any one of claims 11 to 15, further comprising an analysis step of performing. The liquid is ultrapure water,
In the decomposition step, an acid solution, an alkali solution, or an organic solvent is added to ultrapure water in which the generated fine particles are collected, and the fine particles are dispersed. The component analysis method according to any one of claims 11 to 16, wherein the component is analyzed.

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