Sample introduction device, inductively coupled plasma analysis device and analysis method

Abstract

Sample introduction device (1) comprising: a nebulizer (16) which atomizes a sample liquid; a spray chamber (10) having one end into which a spray nozzle portion of the nebulizer (16) is inserted, and another end from which at least a portion of the sample liquid droplets sprayed by the spray nozzle portion are discharged to the outside; and a unit (17) for radiating heating electromagnetic waves, which is arranged outside the spray chamber (10), wherein the heating electromagnetic wave radiating unit (17) radiates heating electromagnetic waves from outside the spray chamber (10) toward at least a part of the spray chamber (10) other than a part into which the spray nozzle portion of the nebulizer (16) is inserted, wherein the spray nozzle portion of the nebulizer (16) is free from direct irradiation of the heating electromagnetic waves, and wherein the heating electromagnetic wave radiating unit (17) has a ring shape, and the spray chamber (10) is inserted into a hollow part of the ring shape; and wherein the unit (17) for radiating heating electromagnetic waves having the ring shape is adapted to radiate heating electromagnetic waves towards the interior of a ring.

Description

Field of the invention

[0001] The present invention relates to a sample introduction device, an inductively coupled plasma analysis device and an analysis method. Discussion of the background

[0002] In order to atomize a sample liquid and introduce the atomized sample into an analysis unit in the form of liquid droplets, a sample introduction device including a nebulizer (atomizer) and a spray chamber is provided in various analysis devices (see, for example, PTL1).

[0003] JP05190136A (PTL2) shows a heating means for heating the wall of a spray chamber opposite the injection port of an atomizer, which is installed by a heater.

[0004] JP05256837A (PTL3) shows an infrared emitter mounted between a thin tube for spraying a sample solution and a narrow opening for receiving ions in a high vacuum region to irradiate liquid droplets with infrared rays.

[0005] DE112018002448T5 (PTL4) shows a spray chamber including a region with a sample inlet opening into which a gas stream containing sample droplets atomized by a nebulizer is introduced, a region with an outlet opening which discharges at least a portion of the gas stream introduced into the sample inlet opening region to the outside, and a flow passage tube section which has the sample inlet opening region at one end region thereof and the outlet opening region at the other end region thereof and serves as a flow passage for the introduced gas stream, wherein the flow passage tube section includes a first tube section having the outlet opening region at one end region thereof and a second tube section having the sample introduction tube section at one end region thereof, the spray chamber includes a double tube section,formed by overlapping at least a part of the cylindrical portion of the first pipe section and the cylindrical portion of the second pipe section, and an outer side surface of the double pipe section is provided with an additional gas inlet opening and an additional gas inlet pipe section which serves as an introduction channel for introducing an additional gas into the double pipe section through the additional gas inlet opening. PTL1: Japanese patent application JP2008157895A PTL2: Japanese patent application JP05190136A PTL3: Japanese patent application JP05256837A PTL4: German patent application DE112018002448T5 Summary of the invention

[0006] To obtain a reliable analysis result when using an analysis device, it is desirable that the measurement result does not fluctuate excessively, even when the analysis device is continuously used. However, according to a study by the present inventors, it has become apparent that the device described in PTL1 (Japanese Patent Application, JP2008157895A) is not necessarily sufficient in this regard.

[0007] One aspect of the present invention provides a sample introduction device that allows an analysis device to obtain a reliable analysis result.

[0008] One aspect of the present invention relates to a sample introduction device including: a nebulizer that atomizes a sample liquid; a spray chamber having one end into which a spray nozzle portion of the nebulizer is inserted, and another end from which at least a portion of the sample liquid droplets sprayed by the spray nozzle portion are discharged to the outside; and a unit for radiating heating electromagnetic waves, which is arranged outside the spray chamber, wherein the unit for radiating heating electromagnetic waves carries out the radiating of heating electromagnetic radiation from outside the spray chamber towards at least a part of the spray chamber which is a different part than that in which the spray nozzle part of the nebuliser is inserted, wherein the spray nozzle portion of the nebulizer is free from direct radiation of the heating electromagnetic waves, and wherein the unit for radiating heating electromagnetic waves has a ring shape and the spray chamber is inserted into a hollow part of the ring shape; and wherein the unit for radiating heating electromagnetic waves having the ring shape is adapted to radiate heating electromagnetic waves toward the interior of a ring.

[0009] The above-described Japanese patent application JP2008157895A discloses a sample introduction device including means for heating light radiation.

[0010] When sample liquid droplets atomized by a nebulizer and introduced into a chamber are heated by heating light, at least a portion of a solvent enclosed in the sample liquid droplets is allowed to evaporate, resulting in a reduction in the amount of solvent introduced into the analysis unit of an analysis device. The present inventors believe that this can reduce the load on the analysis unit of the analysis device due to the evaporation energy of the solvent, thus resulting in an increase in the intensity of the measurement signal obtained by the analysis unit. However, in the device described in Japanese patent application JP2008157895A, the radiation of the heating light by the radiation aids is performed in a manner to cover the spray nozzle of the nebulizer (see claim 1, Fig. 1, etc. in Japanese Patent Application JP2008157895A). In contrast, in the sample introduction device according to one aspect of the present invention, the radiation of the heating electromagnetic waves from the electromagnetic wave radiation unit is performed toward at least a part other than the part into which the spray nozzle portion of the spray chamber is inserted, the spray nozzle portion of the nebulizer being free from direct radiation of the heating electromagnetic waves, the heating electromagnetic wave radiation unit has a ring shape, and the spray chamber is inserted into a hollow part of the ring shape; and the heating electromagnetic wave radiation unit having the ring shape is configured to perform the radiation of the heating electromagnetic waves toward the inside of a ring.This means that the spray nozzle section of the nebulizer is free from direct exposure to heating electromagnetic waves. The present inventors believe that this design contributes to the fact that a measurement result does not fluctuate excessively even when an analysis device, including the sample introduction device, is continuously used. The details of this fact are described below.

[0011] When the heating light is irradiated in a manner that covers the spray nozzle of the nebulizer, as in the device described in Japanese Patent Application JP2008157895A, it appears that a component trapped in a sample liquid dries at the spray nozzle of the nebulizer and deposits inside or at the tip of the spray nozzle as the irradiation continues. When adherent material such as a deposit and a layered carbide is deposited inside or at the tip of the spray nozzle during analysis by an analysis unit, a fluctuation in the amount of sample liquid droplets sprayed by the nebulizer appears to occur, thus giving rise to a large fluctuation in the measurement results.

[0012] In contrast, in the sample introduction device according to the invention, the spray nozzle section of the nebulizer is free from direct exposure to heating electromagnetic waves. Therefore, it appears possible to reduce fluctuations in the amount of sample liquid droplets sprayed by the nebulizer during analysis by an analysis device and to perform reliable analysis without excessive fluctuations in the measurement results.

[0013] In one embodiment, the above heating electromagnetic waves may include near-infrared rays.

[0014] In one embodiment, the above spray chamber may be made of glass, quartz or a fluororesin.

[0015] In one embodiment, the above unit for radiating the heating electromagnetic waves may radiate the heating electromagnetic waves toward at least a part of the spray chamber which is near the end of the spray chamber into which at least a part of the liquid droplets are discharged.

[0016] According to the invention, the above heating electromagnetic wave radiating unit is annular, and the above spray chamber is inserted into a hollow part of the annular shape.

[0017] In one embodiment, an amount of the sample liquid introduced into the above nebulizer may be equal to or greater than 1 µl / min and equal to or less than 500 µl / min.

[0018] One aspect of the present invention relates to an inductively coupled plasma analysis device including the above sample introduction device and an analysis unit.

[0019] In one embodiment, the above inductively coupled plasma analysis apparatus may include a plasma torch and an injector that introduces a sample to be analyzed into the plasma torch, and an inner diameter of the injector may be equal to or greater than 0.50 mm and equal to or less than 1.50 mm.

[0020] In one embodiment, the above inductively coupled plasma analysis apparatus may further include a gas supply source that supplies argon gas to the plasma torch, and one or more gas supply sources that supply one or more types of gases other than argon gas.

[0021] In one embodiment, the above-described one or more kinds of gases may be selected from the group consisting of nitrogen gas, oxygen gas, and hydrogen gas, and the gas may be supplied to the plasma torch in an amount which is smaller per unit time than an amount of the argon gas.

[0022] In one embodiment, the above inductively coupled plasma analysis device may be an inductively coupled plasma mass spectrometer or an inductively coupled plasma atomic emission spectrometer.

[0023] One aspect of the present invention relates to an analysis method including performing qualitative analysis, quantitative analysis, or qualitative and quantitative analysis of an analysis target sample with the above inductively coupled plasma analysis apparatus.

[0024] In one embodiment, the above analytical method may perform the qualitative, quantitative, or qualitative and quantitative analysis of a metallic constituent in a target analysis sample.

[0025] According to one aspect of the present invention, it is possible to provide a sample introduction device that allows an analysis device to obtain a reliable analysis result. Additionally, according to one aspect of the present invention, it is possible to provide an inductively coupled plasma analysis device including the above sample introduction device and an analysis method using the above inductively coupled plasma device. Brief description of the drawings Fig. 1 is a schematic view (side view) showing an example of a sample introduction device according to one aspect of the present invention; Fig. 2 is a schematic view (side view) showing an example of a spray chamber; Fig. 3A is a schematic view (top view) showing an example of the spray chamber; Fig. 3B is a schematic view (side view) showing an example of the spray chamber; Fig. Fig. 4A is an explanatory view for explaining the arrangement of an additional gas introduction pipe section in the spray chamber shown in Fig. 3A and Fig. 3B is shown; Fig. Fig. 4B is an explanatory view for explaining the arrangement of the additional gas introduction pipe section in the spray chamber shown in Fig. 3A and Fig. 3B is shown; Fig. Fig. 4C is an explanatory view for explaining the arrangement of the additional gas introduction pipe section in the spray chamber shown in Fig. 3A and Fig. 3B is shown; Fig. 5A is a schematic view (top view) showing another example of the spray chamber; Fig. 5B is a schematic view (top view) showing the other example of the spray chamber; Fig. 6 shows the observation results of the signal intensity of In obtained in Example 1 and Comparative Example 1; Fig. Figure 7 shows the relative standard deviations (RSAs) of the signal intensity of In calculated in Examples 2 and 3; Fig. Figure 8 shows the relative intensity ratios of the signal intensity of different analytes (signal intensity with radiation of the heating electromagnetic waves / signal intensity without radiation of the heating electromagnetic waves) obtained in Example 4; Fig. Figure 9 shows the relative standard deviations (RSAs) of the signal intensity of the different analytes obtained in Example 4; Fig. Figure 10 shows the relative intensity ratios of the signal intensity of the different analytes (signal intensity with introduction of N2 / signal intensity without introduction of N2) obtained in Example 5; and Fig. Figure 11 shows the relative standard deviations (RSAs) of the signal intensities of various analytes obtained in Example 5. Description of the embodimentsSample introduction device

[0026] The above sample introduction device will be described in more detail below. The description of the sample introduction device will be given with reference to the drawings. However, the embodiments shown in the drawings are provided for illustration purposes only, and the present invention is not limited to the embodiments.

[0027] Fig. Fig. 1 is a schematic view (side view) showing an example of a sample introduction device according to the present invention. A sample introduction device 1 shown in Fig. 1, includes a spray chamber 10, a nebulizer 16 and a unit 17 for radiating heating electromagnetic waves. Unit for radiating heating electromagnetic waves

[0028] At the Fig. In the sample introduction device 1 shown in FIG. 1, the heating electromagnetic wave irradiation unit 17 is arranged at a position where a spray nozzle portion at the tip of the nebulizer 16 is not irradiated with heating electromagnetic waves. It appears that such an arrangement of the heating electromagnetic wave irradiation unit can contribute to preventing excessive fluctuation of a measurement result even when an analysis device including the sample introduction device is continuously used. In addition, at least a part of a solvent contained in the droplets of the sample liquid introduced from the nebulizer can be evaporated by irradiation with the heating electromagnetic waves from the heating electromagnetic wave irradiation unit.It appears that this can reduce the load on the analysis unit of the analyzer due to the evaporation energy of the solvent, thus increasing the intensity of the measurement signal obtained by the analysis unit. Furthermore, the placement of auxiliary devices for irradiating heating electromagnetic waves outside the spray chamber can prevent the occurrence of contamination inside the spray chamber caused by these auxiliary devices.

[0029] The heating electromagnetic waves emitted by the heating electromagnetic wave emitting unit may be various electromagnetic waves capable of heating the liquid droplets of a sample liquid flowing through the interior of the spray chamber. Examples of the electromagnetic waves may include infrared rays, microwaves, and the like. Here, "infrared rays" represent electromagnetic waves with a wavelength of 780 nm to 1000 µm and include near-infrared radiation (with a wavelength of 780 nm to 2 µm), mid-infrared radiation (with a wavelength of greater than 2 µm to 4 µm), and far-infrared radiation (with a wavelength of greater than 4 µm to 1000 µm). "Microwaves" represent electromagnetic waves with a wavelength of 1 cm to 10 cm.In one embodiment, the heating electromagnetic waves radiated from the heating electromagnetic wave radiating unit are preferably electromagnetic waves capable of heating the liquid droplets of a sample liquid flowing through the spray chamber without raising the temperature of the spray chamber (or while reducing the amount of temperature rise of the spray chamber). This is because contamination can be prevented from being caused on the inside of the spray chamber when a contaminant leaks out of the spray chamber while raising the temperature of the spray chamber. In this regard, the heating electromagnetic waves preferably include near-infrared rays, and are more preferably near-infrared rays.

[0030] The heating electromagnetic wave radiating unit has a ring shape. The spray chamber is inserted into the hollow part of the ring shape. The heating electromagnetic wave radiating unit with the ring shape radiates heating electromagnetic waves toward the interior of a ring. An example of the heating electromagnetic wave radiating unit according to such an embodiment is the heating electromagnetic wave radiating unit 17 shown in Fig. 1. The unit for radiating heating electromagnetic waves may, for example, have a structure in which a plurality of electromagnetic wave radiating devices (for example, infrared lamps, microwave generating sources, or the like) are arranged circumferentially inside an annular part of a casing, a structure in which annular electromagnetic wave radiating devices are arranged inside the annular part of a casing. Furthermore, the inner wall of the annular part of a casing may be made of a material that can reflect heating electromagnetic waves.However, the electromagnetic wave radiating unit of the above sample introduction device only needs to be capable of radiating the heating electromagnetic radiation toward at least a portion of the spray chamber other than the portion into which the spray nozzle portion of the nebulizer is inserted from outside the spray chamber. The heating electromagnetic wave radiating unit can have various shapes and configurations.

[0031] The installation position of the heating electromagnetic wave radiating unit of the above sample introduction device will be described in more detail later. Nebulizer

[0032] As the nebulizer of the above sample introduction device, a nebulizer (also called an atomizer) having a known structure and capable of atomizing liquid droplets can be used. The nebulizer is capable of atomizing a sample liquid introduced into the nebulizer and spraying a gas stream containing the liquid droplets of the atomized sample liquid to be introduced into the spray chamber. The amount of sample liquid to be introduced into the nebulizer only needs to be determined according to the type or the like of an analysis device into which a sample is introduced through the sample introduction device. The introduction amount can be, for example, equal to or greater than 1 µL / min and equal to or less than 500 µL / min.The nebulizer is capable of generating a gas stream containing sample liquid droplets (atomizing a sample), for example, by mixing a sample liquid with a carrier gas and spraying the mixture. Generally, one or two or more types of inert gas are used as the carrier gas. Specific examples of the carrier gas include argon gas.

[0033] A gas stream, including sample liquid droplets, atomized by the nebulizer, is introduced into the spray chamber and flows through the spray chamber. Spray chamber

[0034] The spray chamber of the above sample introduction device only requires that it have a structure that allows liquid droplets to be introduced by a gas flow from one end and at least a portion of the introduced liquid droplets to be discharged to the outside from the other end. According to such a structure, it is possible to introduce the liquid droplets of a sample liquid together with a gas flow from one end of the spray chamber and discharge at least a portion of the liquid droplets of the introduced sample liquid to the outside from the other end.In general, a spray chamber is capable of selecting the particle size of liquid droplets according to a gravity difference by utilizing a weight difference based on a difference in the particle sizes of the liquid droplets and playing a role in the selective introduction of fine liquid droplets into an analytical device.

[0035] The above spray chamber can be a single tubular component or a component in which two or more components are combined. Considering the permeability of heating electromagnetic waves, the spray chamber is preferably made of glass, quartz, or a fluororesin.

[0036] An example of the spray chamber of the above sample introduction device will be described below with reference to the drawings. However, the spray chamber of the above sample introduction device is not limited to the illustrated example.

[0037] Fig. Figure 2 is a schematic view (side view) showing an example of the spray chamber. The spray chamber 10, shown in Fig. 2, is composed of a flow path pipe section 13, including a first pipe section 11 and a second pipe section 12. In the spray chamber 10 according to a Fig. In the embodiment shown in Figure 2, the first pipe section 11 is connected to an analysis unit, which will be described in detail later. Specifically, the first pipe section 11 is connected to an inlet section 14 of the analysis unit, which is a section positioned on the side closest to the spray chamber, via a connecting element 15. Furthermore, in the embodiment shown in Fig. 2, the second pipe section 12 is connected to the nebulizer 16. The Fig. 3A and Fig. 3B are schematic views showing only the spray chamber. Fig. 3A is a plan view and Fig. 3B is a side view. In the Fig. 3A and Fig. In Figure 3B, the dashed lines indicate a thickness and not a double pipe.

[0038] The spray chamber 10, shown in the Fig. 3A and Fig. 3B, is composed of the flow path tube section 13 having an outlet port section 110 at one end and a sample introduction port section 121 at the other end. The flow path tube section 13 is formed from the first tube section 11 and the second tube section 12. The first tube section 11 is composed of the outlet port section 110, a conical part 111, and a cylindrical part 112. On the other hand, the second tube section 12 is composed of a cylindrical part 120 and the sample introduction port section 121. When the cylindrical part 12 of the first tube section 11 and the cylindrical part of the second tube section 12 are at least partially overlapped and joined together, a double tube section 100 is formed.Accordingly, the inner wall surface of the double pipe space of the double pipe section 100 corresponds to the outer side surface of the cylindrical part 120 of the second pipe section 12, and the outer wall surface of the double pipe space of the double pipe section 100 corresponds to the inner wall surface of the cylindrical part 112 of the first pipe section 11.

[0039] Next, the first pipe section and the second pipe section are described in more detail.

[0040] In the Fig. 3A and Fig. 3B, the first tube section 11 has the outlet opening section 110 at one end, and the outlet opening section 110 communicates with the conical part 111. The conical part 111 has a conical shape whose inner diameter decreases toward the outlet opening section. The conical part 111 communicates with the cylindrical part 112, including the other end of the first tube section.

[0041] On the other hand, in the second pipe section 12, the cylindrical part 120 including one end of the second pipe section and the sample introduction port part 121 including the other end thereof are in communication with each other.

[0042] The flow path pipe section 13 is formed by the thus structured first pipe section 11 and second pipe section 12. In addition, the double pipe section 100 is formed when the cylindrical parts of both pipe sections are overlapped with each other at the junction between the first pipe section 11 and the second pipe section 12. The double pipe section represents the section between an opening at the end of the cylindrical part of the first pipe section and an opening at the end of the cylindrical part of the second pipe section. Accordingly, both ends of the double pipe section are openings, and an imaginary plane surrounded by the openings is referred to below as a bottom surface. In a Fig. 3A and Fig. In the embodiment shown in Fig. 3B, the first pipe section 11 and the second pipe section 12 are separate components. When the cylindrical part 120 of the second pipe section 12 is inserted into the opening at the end of the cylindrical part 112 of the first pipe section 11, both pipe sections are connected to each other to form the flow path pipe section 13. For example, if the cylindrical part 112 of the first pipe section 11 narrows into a tapered shape at the end and the inner diameter of the opening at the end has substantially the same shape as that of the outer diameter of the opening at the end of the cylindrical part 120 of the second pipe section 12, it is possible to prevent the leakage of auxiliary gas introduced into the double pipe section 100 formed by connecting both pipe sections to the outside from the junction between both pipe sections.Alternatively, the sealing effect of the connection can be ensured by a sealing element or the like. Regarding the tightness of the connection, it is not necessary to completely prevent leakage of the auxiliary gas. The leakage of the auxiliary gas is permitted to the extent that the flow of the auxiliary gas introduced into the double-tube section as a gas stream is not disrupted. Alternatively, the first tube section and the second tube section can be integrally formed to form the flow path tube section.

[0043] The double-pipe section 100 has an opening on its outer side surface, that is, on the outer side surface of the cylindrical part 112 of the first pipe section 11. The opening is an opening (auxiliary gas introduction port) for introducing the auxiliary gas into the double-pipe section (that is, the space surrounded by the inner wall surface and the outer wall surface of the double-pipe section). A auxiliary gas introduction pipe section 101 serves as an introduction path for introducing the auxiliary gas into the double-pipe section through the opening. Since the auxiliary gas is introduced from the auxiliary gas introduction portion into the double-pipe section through the opening, the introduced auxiliary gas can rotate inside the double-pipe section and generate a spiral gas flow (auxiliary gas flow) toward the conical part 111 of the first pipe section 11.The presence of the conical portion, whose inner diameter decreases toward the outlet port section of the spray chamber, can also contribute to the auxiliary gas flow becoming a spiral gas flow. The thus generated auxiliary gas flow can be directed spirally toward the outlet port section, along the wall surface of the conical portion. Such an auxiliary gas flow can prevent sample liquid droplets from adhering to the wall surface of the conical portion. In addition, the auxiliary gas flow can be directed toward the outlet port section while entraining the sample liquid droplets.

[0044] In one in the Fig. 3A and Fig. 3B, the cylindrical part 112 of the first pipe section 11 has an opening for waste liquid and a waste liquid pipe section 113 for discharging waste liquid through the waste liquid opening, adjacent to the auxiliary gas introduction opening. The waste liquid pipe section 113 can also serve as a waste liquid path for discharging waste liquid from the inside to the outside of the double pipe section 100. Furthermore, in the embodiment shown in Fig. 3A and Fig. 3B, the second pipe section 12 further includes a waste liquid pipe section 122. The waste liquid pipe section 122 can serve as a waste liquid path for discharging waste liquid from the inside to the outside of the second pipe section 12.

[0045] Next, the corresponding parts of the above spray chamber are described in further detail.

[0046] The Fig. 4A to 4C are views to show the arrangement of the auxiliary gas introduction pipe section in the spray chamber shown in the Fig. 3A and Fig. 3B, to explain. Fig. 4A is a view obtained by adding arrows to explain the Fig. Top view shown in Figure 3A. Fig. 4B is a cross-sectional view of a section including the auxiliary gas introduction tube section of the double tube section. Fig. 4C is a view obtained by adding arrows to explain the Fig. 3B. The arrows in the Fig. 4A to 4C show the following directions. An X direction represents the central axis direction of the auxiliary gas introduction pipe section. A Y direction represents the central axis direction of the cylindrical part of the first pipe section and also corresponds to the central axis direction of the conical part of the first pipe section and the central axis direction of the cylindrical part of the second pipe section. Furthermore, the Y direction also corresponds to the central axis direction of the flow path pipe section. A Z direction represents the central axis direction of the sample introduction port section.

[0047] The Fig. 5A and Fig. 5B are a top view and a side view, respectively, of a spray chamber according to another embodiment. In one embodiment, shown in FIGS. Fig. 5A and Fig. 5B, a spray chamber is the same spray chamber as the one in the Fig. 2, 3A, 3B, and 4A to 4C, except that the arrangements of an auxiliary gas introduction pipe section 101 and a sample introduction port section 121 are different. The description of the correspondences is omitted.

[0048] An angle θ1 formed by the X-direction and the Y-direction is 90° in a direction Fig. 4A to 4C, and is 110° in a configuration shown in the Fig. 5A and Fig. 5B. The angle θ1 is defined to be in the range of 0° to 180°. The angle θ1 is preferably in the range of 90° to 130° from the viewpoint of smoothly rotating the gas flow of the auxiliary gas introduced from the auxiliary gas introduction pipe section inside the double pipe section. Further, the auxiliary gas introduction port may be provided at any position on the outer side surface of the double pipe section. For example, the auxiliary gas introduction port may be provided at a position near the second pipe section or at a position near the first pipe section relative to the center of the outer side surface of the double pipe section, or may be provided at a position where the center of the auxiliary gas introduction port corresponds to the center of the outer side surface of the double pipe section.In order to smoothly rotate the flow of the auxiliary gas introduced from the auxiliary gas introduction pipe section inside the double pipe section, the auxiliary gas introduction port is preferably provided at a location close to the second pipe section on the outer side surface of the double pipe section. It is more preferable that the auxiliary gas introduction port is provided at a location closer to the second pipe section.

[0049] In order to smoothly rotate the flow of the auxiliary gas introduced from the auxiliary gas introduction pipe section inside the double pipe section, the length of the double pipe section, that is, the shortest distance between a bottom surface on the first pipe section side and a bottom surface on the second pipe section side, is preferably in the range of 10.0 mm to 30.0 mm. Furthermore, the diameter of the auxiliary gas introduction port is preferably in the range of 0.1 mm to 3.0 mm. The same applies to the diameter of the waste liquid port.

[0050] In the first pipe section, the tapered portion is a portion located between the cylindrical portion and the exhaust port portion, and has an inner diameter that decreases toward the exhaust port portion side. In the first pipe section, a position where a change in the inner diameter starts on the cylindrical portion side and continues toward the exhaust port portion side is a portion of the tapered portion, and a position where the change in the inner diameter ends is the other end of the tapered portion. The shortest distance from one end to the other end of the tapered portion is called the length of the tapered portion.The ratio of the length of the conical part to the maximum inner diameter of the conical part (length / maximum inner diameter) is preferably equal to or greater than 0.3 in order to reduce the loss of sample liquid droplets in the conical part due to wall adhesion. When the ratio is equal to or greater than 0.3 (particularly equal to or greater than 0.5, and even more preferably equal to or greater than 0.8), it is possible to make the gas flow of the auxiliary gas spiral more smoothly in the conical part. Furthermore, as the ratio increases, the length of the conical part relative to the maximum inner diameter of the conical part becomes longer. For example, the ratio may be equal to or less than 4.0 or equal to or less than 3.5. However, as the ratio increases with an increase in the length of the conical part, the overall length of the spray chamber increases, and its size also increases.On the other hand, a study by the present inventors shows that a change in analytical sensitivity is no longer noticeable even by increasing the length of the conical part when the ratio is greater than 3.0. Therefore, the ratio is preferably equal to or less than 3.0 with a view to both improving analytical sensitivity and reducing the size of the spray chamber.

[0051] The maximum inner diameter of the conical part of the first pipe section is preferably in the range of, for example, 25.0 mm to 65.0 mm. The maximum inner diameter of the conical part is equal to the inner diameter of the cylindrical part that communicates with the conical part. As described above, the cylindrical part may have a shape that tapers towards a tapered shape at its end. In this case, the inner diameter of the cylindrical part represents the maximum inner diameter of the cylindrical part. Furthermore, the minimum inner diameter of the conical part of the first pipe section is preferably in the range of, for example, 5.0 mm to 10.0 mm. In the conical part, the shape of a cross-section passing through its central axis is not necessarily part of a perfect triangle. At least part of the shape of the cross-section may include a curve.

[0052] In the above spray chamber, the outer diameter of the cylindrical part of the second pipe section is smaller than the inner diameter of the second pipe section and the cylindrical part of the first pipe section. Therefore, the double pipe section can be formed by at least partially overlapping the cylindrical part of the first pipe section and the cylindrical part of the second pipe section. The difference between the inner diameter of the cylindrical part of the first pipe section and the outer diameter of the cylindrical part of the second pipe section is preferably in the range of 1.0 mm to 6.0 mm.When the difference is in the range of 1.0 mm to 6.0 mm, the space surrounded by the inner wall surface of the cylindrical part of the first pipe section and the outer wall surface of the cylindrical part of the second pipe section, that is, the width of the space into which the auxiliary gas is introduced, may be in the range of 0.5 mm to 3.0 mm. The space having a width equal to or greater than 0.5 mm is preferable from the viewpoint of facilitating the discharge of a waste liquid from the double pipe section. Furthermore, the space having a width equal to or less than 3.0 mm is preferable from the viewpoint of smoothly rotating the gas flow of the auxiliary gas introduced from the auxiliary gas introduction pipe section inside the double pipe section. For example, the inner diameter of the cylindrical part of the second pipe section is preferably in the range of, for example, 20.0 mm to 60.0 mm.For example, if the inner diameter of the cylindrical part of the second pipe section is equal to or larger than 20 mm, it is possible to effectively prevent collisions between sample liquid droplets in a gas stream introduced from the sample introduction port section and reduce the loss of liquid droplets due to collisions between the liquid droplets. Furthermore, it is preferable that the inner diameter of the cylindrical part of the second pipe section is equal to or smaller than 60 mm in view of miniaturizing the second pipe section and miniaturizing the spray chamber.

[0053] The second tube section has the cylindrical part and the sample introduction opening section and is preferably composed of the cylindrical part and the sample introduction opening section. In a Fig. 4C, an angle θ2 formed by the central axis direction (Z direction) of the sample introduction port portion 121 and the central axis direction (Y direction) of the cylindrical part of the first tube portion is 30°. On the other hand, in an embodiment shown in Fig. 5B, the Z direction is the same direction as the Y direction (that is, the angle θ2 formed by the Z direction and the Y direction is 0°). The angle θ2 is defined in the range of 0° to 90°. If the angle θ2 is 0°, sample liquid droplets do not tend to collide with the wall surface of the cylindrical part of the second pipe section when a gas flow including the sample liquid droplets is introduced into the spray chamber from substantially the same direction as the central axis direction of the sample introduction port section. Thus, it appears that the loss of liquid droplets due to wall surface adhesion in the spray chamber can be further effectively reduced. Accordingly, the Z direction is preferably the same direction as the Y direction from the viewpoint of further improving analytical sensitivity.

[0054] On the other hand, when a gas flow including sample liquid droplets is introduced into the spray chamber from substantially the same direction as the central axis direction of the sample introduction port portion, in a case where the Z direction is inclined with respect to the Y direction, a portion of the sample liquid droplets is prone to colliding with the wall surface of the cylindrical portion of the second pipe portion. Upon collision with the wall surface of the cylindrical portion of the second pipe portion, the liquid droplets may burst into finer liquid droplets. Therefore, the liquid droplets discharged from the spray chamber are likely to be finer. The finer sample liquid droplets are preferable in view of stabilizing the sensitivity of the analysis unit of the analysis device.Accordingly, if sensitivity stabilization is important, the Z direction is preferably inclined relative to the Y direction. For example, the angle θ2 is preferably in the range of 10° to 60°.

[0055] In the above spray chamber, the length of the cylindrical part of the second pipe section is preferably in the range of, for example, 10.0 mm to 70.0 mm. At least a part of the cylindrical part forms the double pipe section, and the above length includes the length of the part forming the double pipe section. The cylindrical part of the second pipe section does not have a perfect cylindrical shape, for example, as shown in a Fig. 3B and Fig. 4C, and its lower surface portion on the side of the sample introduction port portion may be inclined with respect to a central axis direction of the cylindrical portion of the second tube portion. In this case, the length of the cylindrical portion represents the shortest length (for example, a length l in Fig. 4C).

[0056] In the above spray chamber, the shape and length of the outlet port portion of the first pipe portion are not specifically limited, as long as the outlet port portion has an opening serving as the outlet port. The shape of the tip of the outlet port portion only needs to be determined according to the shape of the analysis portion, since the tip generally serves as a portion connected to the analysis portion in the analysis device.

[0057] On the other hand, the shape and length of the sample introduction port portion of the second tube portion are not specifically limited, as long as the sample introduction port portion has an opening for introducing a gas stream containing sample liquid droplets from the nebulizer. The sample introduction port portion generally serves as an insertion port portion into which the tip of the nebulizer is inserted. The sample introduction port portion may, for example, have a cylindrical shape, but its shape is not specifically limited, as described above.

[0058] Regarding the total length of the above spray chamber, it is likely that the loss of liquid droplets in the spray chamber can be reduced if the total length is shorter. On the other hand, the particle size selection performance of the spray chamber is likely to be improved if the total length is longer. Taking the above points into consideration, the total length of the above spray chamber is preferably in the range of, for example, 80.0 mm to 200.0 mm. The total length of the above spray chamber represents the shortest distance from one extreme end to the other extreme end of the spray chamber in a side view. For example, the total length of the spray chamber corresponds to a length L in Fig. 4C or a length L in Fig. 5B.

[0059] The above spray chamber is capable of introducing the auxiliary gas from the double-tube section. Thus, it is possible to reduce the loss due to wall surface adhesion of sample liquid droplets. However, due to the particle size selection of the sample liquid droplets based on a gravity difference inside the spray chamber, a portion of a sample liquid introduced as liquid droplets may remain inside the spray chamber without being discharged from the spray chamber. Furthermore, a portion of the sample liquid introduced as liquid droplets may remain inside the spray chamber due to the occurrence of wall surface adhesion. The above spray chamber preferably has at least one waste liquid path for discharging the remaining sample liquid to the outside.For example, a waste liquid path for discharging sample liquid remaining inside the first pipe section may be provided at any location of the first pipe section. In one embodiment, the waste liquid path may be provided at a section constituting the double pipe section. That is, the above spray chamber may include a waste liquid opening and a waste liquid pipe section serving as a waste liquid path for discharging waste liquid to the outside from the inside of the double pipe section via the waste liquid opening on the outer side surface of the double pipe section (for example, the waste liquid pipe section 113 in FIG. Fig. 3B). Furthermore, the above spray chamber may have a waste liquid opening on the outer side surface of the second pipe section for discharging the sample liquid remaining in the second pipe section, and a waste liquid pipe section serving as a waste liquid path for discharging a waste liquid from the inside of the second pipe section to the outside (for example, the waste liquid pipe section 122 in Fig. 3B).

[0060] In the present invention and the present specification, a "cylinder" described with reference to the cylindrical part is not limited to one having a perfect cylindrical shape, and also includes an embodiment in which an end having a continuous cylindrical shape includes a portion having a different inner diameter as described above. A "cone" described with reference to the conical part is not limited to one having a perfect conical shape as described above. Furthermore, "substantially equal," which describes the positional relationship between two directions, and "substantially equal," which describes the sizes of two diameters, include not only perfect agreement but also a generally allowable error range.The error range represents, for example, an error range within a range of 0.1° with respect to the positional relationship between two directions, and represents, for example, a range within 1% with respect to the sizes of two diameters.

[0061] The first pipe section and the second pipe section described above can be members made of any materials. Preferred materials include various glasses, quartz, a fluororesin, various resins classified as engineering or super-engineering plastics, or the like in view of chemical resistance such as acid resistance and alkali resistance. Examples of the fluororesin may include various fluororesin such as polytetrafluoroethylene. Examples of engineering plastics may include various engineering plastics such as polycarbonate (PC). Examples of super-engineering plastics may include various super-engineering plastics such as polyetheretherketone (PEEK). For the above reason, the first pipe section and the second pipe section are preferably made of glass, quartz, or fluororesin.Furthermore, the first pipe section and the second pipe section may be components comprising a single pipe structure. The first and second pipe sections may be manufactured according to a known forming method.

[0062] The above-described heating electromagnetic wave radiating unit radiates heating electromagnetic waves toward at least a portion of the spray chamber other than the portion into which the spray nozzle portion of the nebulizer is inserted. The heating electromagnetic wave radiating unit can radiate heating electromagnetic waves toward any portion of the spray chamber other than the portion into which the spray nozzle portion of the nebulizer is inserted. In one embodiment, the heating electromagnetic wave radiating unit preferably radiates heating electromagnetic waves toward at least a portion of the spray chamber located near the end of the spray chamber into which at least a portion of a gas stream introduced by the nebulizer is discharged.Assuming that the shortest distance from one outermost end to the other outermost end is L and the position of L / 2 is a central part in a side view of the spray chamber, then the part of the spray chamber which is near the end represents at least a part of an area from the position of L / 2 to the end to which at least a part of the gas flow is discharged. This part is also referred to below as the "rear part". On the other hand, the part of the spray chamber which is near the end into which the gas flow from the nebulizer is introduced represents at least a part of an area from the end to the position of L / 2. This part is also referred to below as the "front part".It appears that radiating heating electromagnetic waves toward the rear portion is preferable in terms of preventing the occurrence of condensation inside the spray chamber due to a decrease in temperature after the liquid droplets of a sample liquid enclosed in the gas flow are heated. The ability to prevent condensation is preferable in terms of reducing fluctuation in the signal intensity of a signal in the analysis device. It is preferable in one embodiment to radiate heating electromagnetic waves toward the rear portion only, and in another embodiment, it is preferable to radiate the heating electromagnetic waves toward both the rear and front portions.

[0063] The above sample introduction device can be suitably used to atomize a sample liquid and introduce the atomized sample liquid into various analysis devices. Inductively coupled plasma analysis device

[0064] One aspect of the present invention relates to an inductively coupled plasma analysis apparatus (hereinafter also referred to simply as "analysis apparatus") including the above sample introduction apparatus and the analysis unit.

[0065] The details of the sample introduction device included in the above analysis apparatus are described above.

[0066] The above analysis device is an inductively coupled plasma analysis device and may include a plasma torch in at least the analysis unit. For example, the inlet section 14 of the Fig. The analysis device shown in Figure 2 is a section positioned closest to the sample introduction device in the analysis unit and can serve as the inlet section of the plasma torch. The plasma torch is, for example, a section that performs ionization using an inductively coupled plasma mass spectrometer (ICP-MS) or an inductively coupled plasma atomic emission spectrometer (ICP-AES), which is an example of the inductively coupled plasma analysis device.

[0067] As the installation angle of the above sample introduction device in the analysis device, there is an angle θ3 formed between the horizontal direction (for example, an H direction in Fig. 2) an installation surface on which the sample introduction device is installed and the central axis direction (for example, a Y direction in Fig. 2) the spray chamber, preferably in the range of 0° to 90° (that is, from an angle parallel to the horizontal direction of the installation surface to an angle perpendicular to the horizontal direction of the installation surface). This makes it possible to improve the particle size selection performance by allowing liquid droplets with a large liquid droplet particle size introduced into the spray chamber from the nebulizer to fall by gravity to select a particle size. The angle θ3 is defined in the range of 0° to ±90°. If the angle θ3 is negative, the spray chamber is installed so that its rear part is below its front part. If the angle θ3 is positive, the spray chamber is installed so that its front part is below its rear part.Furthermore, one or more waste liquid ports for discharging sample liquid remaining inside the outlet port portion may be provided at any location on the outer side surface of the outlet port portion of the spray chamber. Particularly when the angle θ3 assumes a negative value, such waste liquid ports are preferably provided on the outer side surface of the outlet port portion of the spray chamber.

[0068] Considering both aspects of the efficiency of introducing a sample into the analysis unit and the particle size selection performance, the angle θ3 is more preferably in a range of 20° to 90°, more preferably in a range of 20° to 70°, particularly preferably in a range of 20° to 50°, and most preferably in a range of 20° to 30°.

[0069] The inlet port of the plasma torch may include an injector. Sample liquid droplets introduced by the above sample introduction device may be introduced into the plasma torch after passing through the injector. In view of more stable introduction of the sample liquid droplets into the central part of the plasma torch, the inner diameter of the injector is preferably equal to or less than 1.50 mm, more preferably equal to or less than 1.20 mm, even more preferably equal to or less than 1.00 mm, particularly preferably equal to or less than 0.90 mm, and most preferably equal to or less than 0.80 mm. In view of the efficiency of introducing the sample liquid droplets, the inner diameter is preferably equal to or greater than 0.50 mm.

[0070] An inductively coupled plasma analysis device generally includes a gas supply source for supplying a plasma torch with gas for plasma generation. Argon gas is generally used as the plasma generation gas. Accordingly, the above analysis device may also include a gas supply source for supplying argon gas to the plasma torch. Further, in one embodiment, the above analysis device may include, in addition to the gas supply source for supplying argon gas, gas supply sources for supplying the plasma torch with one or more types of gas other than argon gas. Introducing the other gas into the plasma torch is preferable in view of increasing the electron density in the plasma and accelerating ionization or improving the signal intensity with the introduction of gas having a different viscosity or heat capacity.From the above viewpoints, the other gas is preferably supplied to the plasma torch in an amount smaller than that of argon gas supplied per unit time as the plasma generation gas. Further, in one embodiment, such a gas may be supplied into the spray chamber. Examples of the gas may include one type or two or more types of gas selected from the group consisting of nitrogen gas, oxygen gas, and hydrogen gas. The amount of argon gas supplied to the plasma torch per unit time as the plasma generation gas may be, for example, 16 L / min to 20 L / min. On the other hand, the amount of the other gas supplied to the plasma torch may be, for example, 1 ml / min to 30 ml / min. The argon gas for plasma generation and the other gas may be supplied to the plasma torch via the same gas flow path or via different gas flow paths.

[0071] A target sample, enclosed in sample liquid droplets introduced into the plasma torch, is ionized by the plasma generated at the tip of the plasma torch. Specific examples of inductively coupled plasma analysis devices include ICP-MS and ICP-AES. For example, in the case of ICP-MS, an ion generated by the ionization is introduced into a mass spectrometer, subjected to mass selection by the mass spectrometer, and detected by an ion detector. Thus, it is possible to perform qualitative analysis based on the mass of an ion detected by the ion detector and quantitative analysis based on the signal intensity of ions of a given mass. Analysis methods

[0072] One aspect of the present invention relates to an analysis method including performing the qualitative analysis, the quantitative analysis, or the qualitative and quantitative analysis of an analysis target sample with the above inductively coupled plasma analysis apparatus.

[0073] At the Fig. In the sample introduction device shown in Figure 2, when a gas stream including sample liquid droplets flows through the flow path tube section, make-up gas is introduced from the make-up gas introduction section. Thus, as described above, the introduced make-up gas can rotate inside the double-tube section and generate a spiral gas flow (make-up gas flow) toward the conical part of the first tube section. For example, the various gases explained as examples of carrier gases can be used as the make-up gas. For example, the make-up gas can be introduced from a make-up gas supply source into the double-tube section via the make-up gas introduction section and the make-up gas introduction port after the make-up gas supply source and the make-up gas introduction section are connected to each other by a pipe such as a resin pipe.For synthetic resin pipes, a pipe made of fluororesin such as polytetrafluoroethylene is suitable in terms of durability. The flow rate of the auxiliary gas can range from 0.3 l / min to 0.5 l / min, for example, but it only needs to be adjusted appropriately, taking into account the width of the space of the double-pipe section into which the auxiliary gas is introduced, the size of the conical part, etc. Therefore, the flow rate of the auxiliary gas is not limited to the above range.

[0074] A gas stream containing sample liquid droplets discharged from the spray chamber is introduced into the analysis unit of the above analysis device to perform qualitative analysis and / or quantitative analysis. The details of a specific example or the like of the analysis unit are described above. Examples of a component of an analysis target may include various metal components, such as heavy metals and the like, as well as non-metal components.

[0075] For example, in the analysis method according to one aspect of the present invention described above, it is possible to perform the analysis of the metal components of silicon samples for various silicon samples, such as various silicon wafers used as semiconductor substrates, etc., and single crystal ingots for cutting silicon wafers, and to evaluate the presence or absence and / or extent of contamination by metallic impurities.Since contamination by metallic impurities can cause failure of semiconductor devices, it is desirable to understand the presence or absence and / or extent of metallic impurities and to reject a silicon wafer contaminated by metallic impurities as a defective item, change the manufacturing conditions, or replace or repair a manufacturing device to reduce metallic impurity contamination. In recent years, higher-quality semiconductor substrates have been demanded for high device performance, etc. To meet such demands, it is desirable to reduce metallic impurity contamination of silicon samples. For example, the above analysis method is suitable for a method for analyzing the metal components of various silicon samples.Using the above analysis method, for example, it is possible to perform the qualitative analysis of a metal component as an evaluation of metallic impurity contamination in a silicon sample. When evaluating metallic impurity contamination in a silicon sample, a sample liquid obtained by dissolving part or all of the silicon sample, that is, an evaluation target or a sample liquid obtained by inspecting the surface of a silicon sample with a collecting liquid such as an acid solution and causing the collecting liquid to absorb metallic components adhering to the surface, can be introduced into a nebulizer after pretreatment such as dilution with an acid solution or the like, where necessary, to be subjected to metallic component analysis.According to an analysis result thus obtained, it is possible to evaluate the presence or absence or extent of contamination by various metallic impurities, such as contamination by metallic impurities of parts of a surface layer, contamination by bulk metal contamination, and surface contamination by metallic impurities in a silicon sample.

[0076] However, the present invention is not limited to the evaluation of contamination by metallic impurities of a silicon sample, but is applicable to the analysis of components in various fields. Examples

[0077] The present invention will be further described below based on examples. However, the present invention is not limited to the embodiments illustrated in the examples.

[0078] In the following examples, a pipe made of polytetrafluoroethylene was connected to the auxiliary gas introduction pipe section of a spray chamber for introducing gas, and a pipe made of polyvinyl chloride was connected to a waste liquid pipe section for discharging waste liquid. Furthermore, the first and second pipe sections of the spray chamber in the following examples were made of glass. Example 1

[0079] The spray chamber of a commercially available, double-focusing ICP-MS was replaced by a spray chamber with the Fig. 5A and Fig. 5B, except that an angle θ1 was 90° to prepare the ICP-MS of Example 1. In the ICP-MS of Example 1, the angle θ1 was 90°, an angle θ2 was 0°, an angle θ3 was 30°, the maximum inner diameter of the conical part was 45.0 mm, the ratio of the length of the conical part to the maximum inner diameter of the conical part (length / maximum inner diameter) was 0.5, the length of a double-tube section was 20.0 mm, the diameters of an auxiliary gas introduction port and the waste liquid ports of the double-tube section and the second tube section were 3.0 mm, the inner diameter (maximum inner diameter) of the cylindrical part of the first tube section was 45.0 mm, the outer diameter of the cylindrical part of the second tube section was 42.0 mm, and the total length of the spray chamber was 130.0 mm.

[0080] At a rear end on the outside of the spray chamber, a unit for radiating heating electromagnetic waves, having a ring shape, was installed as shown in Fig. 1. The unit for radiating heating electromagnetic waves consisted of a plurality of near-infrared lamps arranged in a circumferential direction inside a ring-shaped cover.

[0081] As a sample liquid, a hydrofluoric acid (HF solution) was prepared, including 1 ppb (V / V) of In and 2000 ppm (V / V) of Si, and having an HF concentration of 1 mass%.

[0082] In the above ICP-MS, the sample liquid was introduced into a nebulizer at an introduction rate of 100 µL / min. The sample liquid was then atomized by the nebulizer using a carrier gas (argon gas, at a flow rate of 0.75 L / min) to generate a gas flow containing the sample liquid droplets. The gas flow containing the sample liquid droplets was introduced into the flow path tube section of the spray chamber from the sample introduction tube section of the spray chamber. Near-infrared rays were continuously emitted from the heating electromagnetic wave radiating unit while the gas flowed through the flow path tube section. In addition, argon gas was continuously introduced from the auxiliary gas introduction tube section into the double-tube section via the auxiliary gas introduction port at a flow rate of approximately 0.4 L / min.In this way, the signal intensity of In output from the ICP-MS was observed. From the observation results thus obtained, the relative intensity ratio of the In intensity to the near-infrared irradiation time was plotted as a relative intensity ratio to generate a graph, assuming that the signal intensity at the beginning of near-infrared irradiation (0 min) was 1.0. Comparison example 1

[0083] Except that the installation position of the heating electromagnetic wave radiating unit was shifted to a position where an area on the side of the sample introduction port portion of the cylindrical part of the second pipe portion of the spray chamber and the sample introduction port portion were covered, and that the infrared ray radiation was performed toward a portion into which the spray nozzle portion of the nebulizer was inserted, the signal intensity of In was observed as in Example 1. A graph was generated from the obtained observation results as in Example 1.

[0084] The graphs generated for Example 1 and Comparative Example 1 are shown in Fig. 6.

[0085] From the Fig. From the results shown in Figure 6, it can be confirmed that the relative intensity ratio, that is, the analytical sensitivity of Comparative Example 1, was reduced according to the irradiation time with the near-infrared rays compared to Example 1. This is because the irradiation of the near-infrared rays was performed toward the portion in which the spray nozzle portion of the nebulizer was inserted, and thus Si trapped in the sample liquid was dried at the tip of the spray nozzle portion of the nebulizer to cause clogging in Comparative Example 1. On the other hand, the irradiation of the near-infrared rays was performed toward a portion other than the portion in which the spray nozzle portion of the nebulizer was inserted in Example 1. For this reason, it was possible to prevent a reduction in the analytical sensitivity due to the irradiation of the near-infrared rays. Example 2

[0086] Except that hydrofluoric acid (HF solution) including 1 ppb (v / v) of In and having an HF concentration of 1 mass% was used as the sample liquid, the signal intensity of In was observed as in Example 1. 20 measurement results (the signal intensity of In) were extracted from the obtained observation results, and their relative standard deviation (RSA) was calculated. Example 3

[0087] Except that the installation position of the heating electromagnetic wave radiating unit was shifted to a position where the cylindrical part of the second pipe section of the spray chamber was covered (however, the section into which the spray nozzle section of the nebulizer was inserted was not covered), and that the radiating of the near-infrared rays was performed toward the front part of the spray chamber, the signal intensity of In was observed as in Example 2. 20 measurement results (the signal intensity of In) were extracted from the obtained observation results, and their relative standard deviation (RSA) was calculated.

[0088] The relative standard deviations (RSAs) calculated for Examples 2 and 3 are shown in Fig. 7.

[0089] From the Fig. From the results shown in Figure 7, it can be confirmed that a fluctuation of the signal intensity from Example 2, in which the radiation of the heating electromagnetic waves was carried out toward the rear part of the spray chamber, was more reduced (i.e., a signal with more stable intensity was obtained) compared to Example 3. Example 4

[0090] Except that three types of injectors with different inner diameters (0.75 mm, 1.00 mm, and 1.50 mm) were used as injectors for a plasma torch, and that hydrofluoric acid (HF solution) including 1 ppb (V / V) of each of the analytes Co, Y, Ce, and Ti, and having an HF concentration of 1 mass% was used as the sample liquid, the signal intensity of the analytes was observed in the same manner as in Example 1 using an ICP-MS with the same configuration as that in Example 1. For comparison, the sample liquid was analyzed in a similar manner without performing electromagnetic wave radiation by the heating electromagnetic wave radiation unit to measure the signal intensity of the analytes. The signal intensity of the analytes in Fig. 8 shown respective analytes as a relative intensity ratio relative to the signal intensity without radiation of heating electromagnetic waves (the signal intensity with radiation of the heating electromagnetic waves divided by the signal intensity without radiation of the heating electromagnetic waves).

[0091] In addition, 20 analyte signal intensities obtained by the respective injectors were extracted, and their relative standard deviations (RSAs) were calculated. The calculated results are shown in Fig. 9.

[0092] From the Fig. The results shown in Figure 8 confirm that the signal intensity was increased to a greater extent, meaning that the analytical sensitivity was improved more by the radiation of the heating electromagnetic waves in all cases where the three types of injectors were used than in a case without radiation of the heating electromagnetic waves. Furthermore, the results shown in Fig. The results shown in Figure 8 confirm that the analytical sensitivity was more improved when injectors with smaller inner diameters were used. Furthermore, the results in Fig. The results shown in Figure 9 confirm that signal intensity fluctuation was more effectively prevented when injectors with smaller inner diameters were used. Example 5

[0093] Except that N2 (at a flow rate of 30 ml / min) was introduced into a plasma torch via a different flow path than that used for plasma generation with argon gas (at a flow rate of 18 l / min), and that hydrofluoric acid (HF solution) containing 1 ppb (v / v) of each analyte Co, Y, Ce, and Ti, and having an HF concentration of 1 mass%, was used in an ICP-MS having the same configuration as that of Example 1, the signal intensity of the analytes was measured as in Example 4 (which used an injector with an inner diameter of 1.50 mm). In addition, measurements were performed that differed only in that N2 was not introduced. The signal intensity of each analyte is shown in Fig. 10 as the relative intensity ratio relative to the signal intensity without introduction of N2 (the signal intensity with introduction of N2 divided by the signal intensity without introduction of N2).

[0094] In addition, 20 measurement results (the signal intensity of the respective analyte) were extracted from the measurement results with the introduction of N2, and their relative standard deviations (RSAs) were calculated. The calculated results are shown in Fig. 11.

[0095] From the Fig. The results shown in Figure 10 confirm that the signal intensity was increased to a greater extent, i.e. the analytical sensitivity was improved more by the introduction of N2 in comparison to a case without the introduction of N2 into the plasma torch.

[0096] Furthermore, by comparing the Fig. 11 shown results with a case (without introduction of N2) in which the injector from Fig. 9, having an inner diameter of 1.50 mm, confirm that fluctuation of the signal intensity is more effectively prevented by the introduction of N2 into the plasma torch.

[0097] From the above results, it can be confirmed that it is possible to obtain a reliable analysis result in an inductively coupled plasma analysis apparatus according to one aspect of the present invention.

Claims

[1] Sample introduction device (1) comprising: a nebulizer (16) which atomizes a sample liquid; a spray chamber (10) having one end into which a spray nozzle portion of the nebulizer (16) is inserted, and another end from which at least a portion of the sample liquid droplets sprayed by the spray nozzle portion are discharged to the outside; and a unit (17) for radiating heating electromagnetic waves, which is arranged outside the spray chamber (10), wherein the heating electromagnetic wave radiating unit (17) radiates heating electromagnetic waves from outside the spray chamber (10) toward at least a part of the spray chamber (10) other than a part into which the spray nozzle portion of the nebulizer (16) is inserted, wherein the spray nozzle portion of the nebulizer (16) is free from direct irradiation of the heating electromagnetic waves, and wherein the heating electromagnetic wave radiating unit (17) has a ring shape, and the spray chamber (10) is inserted into a hollow part of the ring shape; and wherein the unit (17) for radiating heating electromagnetic waves having the ring shape is adapted to radiate heating electromagnetic waves towards the interior of a ring. [2] The sample introduction device (1) according to claim 1, wherein the heating electromagnetic waves include near-infrared rays. [3] Sample introduction device (1) according to claim 1 or 2, wherein the spray chamber (10) is made of glass, quartz or a fluororesin. [4] The sample introduction device (1) according to any one of claims 1 to 3, wherein the heating electromagnetic wave radiating unit (17) radiates the heating electromagnetic waves toward at least a part of the spray chamber (10) which is near the end of the spray chamber (10) toward which at least a part of the liquid droplets are discharged. [5] The sample introduction device (1) according to any one of claims 1 to 4, wherein an introduction amount of the sample liquid into the nebulizer (16) is equal to or greater than 1 pl / min and equal to or less than 500 pl / min. [6] An inductively coupled plasma analysis device comprising the sample introduction device (1) according to any one of claims 1 to 5. [7] The inductively coupled plasma analysis apparatus according to claim 6, wherein the apparatus comprises a plasma torch and an injector which introduces an analysis target sample into the plasma torch, and an inner diameter of the injector is equal to or greater than 0.50 mm and equal to or less than 1.50 mm. [8] The inductively coupled plasma analysis apparatus according to claim 7, further comprising a gas supply source that supplies argon gas to the plasma torch, and one or more gas supply sources that supply one or more types of gas other than argon gas. [9] The inductively coupled plasma analysis apparatus according to claim 8, wherein the one or more kinds of gas are selected from the group consisting of nitrogen gas, oxygen gas and hydrogen gas, and the gas is supplied to the plasma torch in an amount smaller than the amount of argon gas per unit time. [10] An inductively coupled plasma analysis device according to any one of claims 6 to 9, which is an inductively coupled plasma mass spectrometer or an inductively coupled plasma atomic emission spectrometer. [11] An analysis method comprising performing a qualitative analysis, a quantitative analysis, or a qualitative and quantitative analysis of an analysis target sample with the inductively coupled plasma analysis device according to any one of claims 6 to 10. [12] The analysis method according to claim 11, which performs a qualitative analysis, quantitative analysis or qualitative and quantitative analysis of a metal component in an analysis target sample.

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