JP2017083346A - Liquid sample analyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid sample analyzer that can increase the analysis accuracy.SOLUTION: The liquid sample analyzer according to the present application includes: a container containing a liquid sample; an electrode in the container; an X-ray source that emits primary X-rays; an agitation member that emits secondary X-rays based on the primary X-rays and agitates the liquid sample; and a detection unit that detects fluorescent X-rays emitted from a concentrated sample of the liquid sample near the electrode, based on the secondary X-rays.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a liquid sample analyzer that analyzes a liquid sample using fluorescent X-rays.

  X-ray fluorescence analysis is often used when analyzing elements contained in substances and their constituent ratios. In this fluorescent X-ray analysis, the substance is analyzed using the fact that the energy of fluorescent X-rays differs depending on the element. For example, Patent Document 1 discloses an analyzer that provides a secondary target in a sample cell and excites atoms of the sample using primary X-rays and fluorescent X-rays generated from the secondary target.

JP 2006-30018 A

  In general, an analysis apparatus is desired to have high analysis accuracy, and an improvement in analysis accuracy is also expected in a liquid sample analysis apparatus that analyzes a liquid sample using fluorescent X-rays.

  The present invention has been made in view of such problems, and an object of the present invention is to provide a liquid sample analyzer that can improve the analysis accuracy.

  The liquid sample analyzer of the present invention includes a container, an electrode, an X-ray source, a stirring member, and a detection unit. The container contains a liquid sample. The electrode is provided on the container. The X-ray source emits primary X-rays. The stirring member emits secondary X-rays based on primary X-rays and stirs the liquid sample. The detection unit detects X-ray fluorescence emitted from the concentrated sample concentrated in the vicinity of the electrode from the liquid sample based on the secondary X-ray.

  According to the liquid sample analyzer of the present invention, the stirring member emits secondary X-rays based on the primary X-rays, and the detection unit detects fluorescent X-rays emitted from the concentrated sample based on the secondary X-rays. As a result, analysis accuracy can be improved.

It is a block diagram showing the example of 1 structure of the washing | cleaning apparatus which concerns on one embodiment of this invention. It is sectional drawing showing the example of 1 structure of the precipitation part which concerns on 1st Embodiment. FIG. 3 is a cross-sectional view illustrating a configuration example of a stirrer illustrated in FIG. 2. It is a schematic diagram showing the example of 1 operation | movement of the analyzer which concerns on 1st Embodiment. It is sectional drawing showing the example of 1 structure of the precipitation part which concerns on a modification. It is sectional drawing showing the example of 1 structure of the precipitation part which concerns on another modification. It is sectional drawing showing the example of 1 structure of the precipitation part which concerns on another modification. It is a fragmentary sectional view showing the example of 1 structure of the support part shown to FIG. 7A. It is sectional drawing showing the example of 1 structure of the precipitation part which concerns on 2nd Embodiment. It is a schematic diagram showing the example of 1 operation | movement of the analyzer which concerns on 2nd Embodiment. It is explanatory drawing showing a spectrum.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The description will be given in the following order.
1. First Embodiment 2. FIG. Second embodiment

<1. First Embodiment>
[Configuration example]
FIG. 1 shows an example of the configuration of a cleaning apparatus 1 to which the liquid sample analyzer according to the first embodiment is applied. In this example, the cleaning apparatus 1 cleans a semiconductor wafer used in a semiconductor manufacturing process, and is configured to be able to measure the content of focused ions contained in the cleaning liquid. The cleaning device 1 includes a cleaning unit 11, a pump 12, a filter 13, and an analysis device 20. The cleaning unit 11, the pump 12, the filter 13, and the analyzer 20 are provided on the flow path 8 through which the cleaning liquid 9 flows.

  The cleaning unit 11 cleans the semiconductor wafer. Specifically, the cleaning unit 11 cleans the semiconductor wafer using the cleaning liquid 9 supplied from the filter 13 and discharges the cleaning liquid 9 used for cleaning. The pump 12 sends the cleaning liquid 9 used for cleaning discharged from the cleaning unit 11 to the filter 13. The filter 13 removes impurities such as dust contained in the supplied cleaning liquid 9.

  With this configuration, the cleaning liquid 9 used for cleaning in the cleaning unit 11 is removed of impurities by the filter 13 and supplied again to the cleaning unit 11. Thus, the cleaning liquid 9 circulates in the order of the cleaning unit 11, the pump 12, and the filter 13, and is reused.

The cleaning liquid 9 used for cleaning often contains ions (for example, copper ions Cu ²⁺ ). Such ions are difficult to remove by the filter 13. Therefore, in the cleaning apparatus 1, the analyzer 20 samples the cleaning liquid 9 at a rate of, for example, once every 10 minutes, and detects the amount of ions contained in the sampled cleaning liquid 9. The analyzer 20 prompts the control device (not shown) of the cleaning device 1 to replace the cleaning liquid 9 when the ion content exceeds a predetermined amount. Thus, in this example, the analyzer 20 is provided to perform process management in the semiconductor manufacturing process.

  The analyzer 20 detects the amount of ions contained in the cleaning liquid 9 using fluorescent X-rays. The analysis device 20 includes a valve 21, a pump 22, a deposition unit 30, a voltage generation unit 23, an X-ray source 24, a detection unit 25, a measurement unit 26, a valve 27, and a control unit 28. doing. The valve 21, the pump 22, the precipitation unit 30, and the valve 27 are provided on the flow path 8.

  The valve 21 is for sampling a part of the cleaning liquid 9 circulating through the cleaning unit 11, the pump 12, and the filter 13. The opening and closing of the valve 21 is controlled by the control unit 28. The pump 22 sends the sampled cleaning liquid 9 to the introduction port 35 of the deposition unit 30.

  The depositing unit 30 deposits ions contained in the cleaning liquid 9 supplied from the introduction port 35.

  FIG. 2 shows a configuration example of the precipitation unit 30. In FIG. 2, in addition to the deposition unit 30, the voltage generation unit 23, the X-ray source 24, and the detection unit 25 are also drawn for convenience of explanation. The deposition unit 30 includes electrodes 31 and 32, a reference electrode 33, a stirrer 90, a mesh unit 37, and a stirring unit 38.

The electrode 31 is a conductive electrode having a property of transmitting X-rays, and deposits ions on the surface thereof. As the electrode 31, for example, a thin film electrode can be used. In this example, the electrode 31 is provided so as to cover the opening provided at the bottom of the container 34 of the deposition part 30. As will be described later, a negative voltage is applied to the electrode 31 by the voltage generator 23. Thereby, cations (for example, copper ions Cu ²⁺ ) contained in the cleaning liquid 9 are concentrated near the electrode 31. Specifically, in the vicinity of the electrode 31, the cations contained in the cleaning liquid 9 may have been attracted as ions. Then, cations contained in the cleaning liquid 9 are deposited on the surface of the electrode 31. In this manner, in the vicinity of the electrode 31, the cations in the cleaning liquid 9 attracted as ions and the precipitates from which cations are deposited constitute a concentrated sample. The electrode 31 is irradiated with X-rays L1 from an X-ray source 24, as will be described later. As a result, the X-ray L1 passes through the electrode 31 and is irradiated to the concentrated sample in the vicinity of the electrode 31. Further, the X-ray L1 transmitted through the electrode 31 is also applied to a stirrer 90 described later. The electrode 31 is preferably made of a material having high X-ray permeability and high chemical resistance. Specifically, the electrode 31 is preferably composed of, for example, a diamond electrode, a glassy carbon electrode, an electrode made of a conductive resin containing carbon, or the like.

  The electrode 32 is an electrode having a coil shape, and includes, for example, platinum. With this shape, the surface area of the electrode 32 can be increased. The reference electrode 33 is an electrode used as a reference when a voltage is applied to the electrodes 31 and 32. For example, the reference electrode 33 includes a so-called silver / silver chloride (Ag / AgCl) electrode. In this example, the reference electrode 33 is provided, but this may be omitted.

  The stirrer 90 has a rod shape, and stirs the cleaning liquid 9 in the precipitation part 30 by rotating in the XY plane. The stirrer 90 also has a function of emitting fluorescent X-rays L3 based on the X-rays L1. In this example, the stirring bar 90 is disposed on the mesh part 37. In this example, the stirrer 90 has a rod shape, but is not limited thereto, and may instead have, for example, a disk shape.

  FIG. 3 shows a configuration example of the stirring bar 90. The stirrer 90 has a magnet 91 and a target 92. The magnet 91 includes a magnetic body, and one of the longitudinal directions (lateral direction in FIG. 3) is an N pole and the other is an S pole. The target 92 emits fluorescent X-rays L3 having energy that can excite atoms to be analyzed based on the X-rays L1. Such a target 92 can be configured to include, for example, an element having an atomic number larger than the atomic number of ions to be analyzed contained in the cleaning liquid 9. Specifically, when the ion to be analyzed is a copper ion, the target 92 can be configured to include zinc, gallium, or the like. The magnet 91 and the target 92 are coated with a film 93. The film 93 is made of, for example, a resin. Thereby, in the precipitation part 30, the material of the magnet 91 and the target 92 is prevented from dissolving in the cleaning liquid 9.

  The net part 37 is provided in the vicinity of the center in the vertical direction (Z direction) of the precipitation part 30 and is made of, for example, a resin. A stirrer 90 is arranged on the mesh part 37. Thereby, in the precipitation part 30, the stirring bar 90 can be arrange | positioned in the position away from the electrode 31 now.

  The stirrer 38 rotates the stirrer 90 in the XY plane by generating a magnetic field in the precipitation part 30.

  With this configuration, the stirrer 90 stirs the cleaning liquid 9 in the precipitation unit 30 by rotating in the XY plane on the mesh unit 37 based on the magnetic field generated by the stirring unit 38. The stirrer 90 emits fluorescent X-rays L3 based on the X-rays L1 emitted from the X-ray source 24. This fluorescent X-ray L3 can excite atoms as an analysis target contained in the concentrated sample in the vicinity of the electrode 31. As described above, the stirrer 90 also functions as an X-ray source for irradiating the concentrated sample near the electrode 31 with X-rays.

  The voltage generation unit 23 (FIG. 1) generates various voltages to be supplied to the deposition unit 30 based on a control signal supplied from the control unit 28. Specifically, the voltage generator 23 applies a negative voltage to the electrode 31 and applies a positive voltage to the electrode 32 with reference to the potential of the reference electrode 33. Thereby, in the precipitation part 30, a part of cation contained in the washing | cleaning liquid 9 precipitates on the surface of the electrode 31. FIG. The voltage generator 23 applies a positive voltage to the electrode 31 and a negative voltage to the electrode 32 with reference to the potential of the reference electrode 33 after the analysis in the analyzer 20 is completed. Thereby, in the precipitation part 30, a concentrated sample can be removed from the vicinity of the electrode 31. FIG.

  The X-ray source 24 emits X-rays L1. Specifically, as shown in FIG. 2, the X-ray source 24 emits X-rays L1 within the emission range R1. That is, the emission range R1 corresponds to a spatial region in which the X-ray L1 travels. Thereby, the X-ray source 24 irradiates the concentrated sample near the electrode 31 via the electrode 31 with the X-ray L1. Similarly, the X-ray source 24 irradiates the stirrer 90 on the mesh portion 37 with X-rays L <b> 1 via the electrodes 31. The X-ray source 24 operates based on a control signal supplied from the control unit 28.

  The detection unit 25 detects the fluorescent X-ray L2, and is configured using, for example, a semiconductor detector or a silicon drift detector (SDD). In this example, the stirrer 90, the electrode 32, and the reference electrode 33 are disposed outside the detection range R2 of the detection unit 25. That is, the detection range R2 corresponds to the detectable space area of the detection unit 25. Thereby, in the precipitation part 30, the detection part 25 reduces the possibility of detecting the scattered X-rays from the stirrer 90, the electrode 32, and the reference electrode 33 and the fluorescent X-rays L3 emitted from the stirrer 90. It has become.

  The measurement unit 26 obtains the content of ions contained in the cleaning liquid 9 based on the fluorescent X-ray L2 detected by the detection unit 25. The measurement unit 26 includes, for example, an amplifier, a pulse height analyzer, a multichannel analyzer, and the like. With this configuration, the measurement unit 26 specifies an element that emits the fluorescent X-ray L2 based on the energy of the fluorescent X-ray L2, and obtains the content of the ions based on the intensity of the fluorescent X-ray L2. It has become. Moreover, the measurement part 26 also has a function which notifies that to the control apparatus (not shown) of the washing | cleaning apparatus 1 when content of ion exceeds predetermined amount.

  The valve 27 is for discharging the cleaning liquid 9 in the precipitation part 30. The opening and closing of the valve 27 is controlled by the control unit 28. The control unit 28 controls operations of the valve 21, the voltage generation unit 23, the X-ray source 24, and the valve 27.

  Here, the analyzer 20 corresponds to a specific example of “liquid sample analyzer” in the present invention. The cleaning liquid 9 corresponds to a specific example of “liquid sample” in the present invention. The electrode 31 corresponds to a specific example of “electrode” in the present invention. The stirrer 90 corresponds to a specific example of “stirring member” in the present invention. The X-ray L1 corresponds to a specific example of “primary X-ray” in the present invention. The fluorescent X-ray L3 corresponds to a specific example of “secondary X-ray” in the present invention. The fluorescent X-ray L2 corresponds to a specific example of “fluorescent X-ray” in the present invention.

[Operation and Action]
Then, operation | movement and an effect | action of the washing | cleaning apparatus 1 of this Embodiment are demonstrated.

(Overview of overall operation)
First, referring to FIGS. 1 and 2, an overall operation outline of the cleaning apparatus 1 will be described. The cleaning unit 11 cleans the semiconductor wafer using the cleaning liquid 9 supplied from the filter 13. The pump 12 sends the cleaning liquid 9 discharged from the cleaning unit 11 and used for cleaning to the filter 13. The filter 13 removes impurities such as dust contained in the supplied cleaning liquid 9. The valve 21 samples a part of the cleaning liquid 9 circulating through the cleaning unit 11, the pump 12, and the filter 13 when being opened. The pump 22 sends the sampled cleaning liquid 9 to the deposition unit 30. For example, the voltage generator 23 applies a negative voltage to the electrode 31 and a positive voltage to the electrode 32 with reference to the potential of the reference electrode 33. The stirring unit 38 rotates the stirrer 90 in the XY plane by generating a magnetic field in the precipitation unit 30. Thereby, the stirrer 90 stirs the cleaning liquid 9 in the precipitation part 30. As a result, cations (for example, copper ions Cu ²⁺ ) contained in the cleaning liquid 9 are concentrated near the electrode 31. Specifically, cations contained in the cleaning liquid 9 are attracted in the vicinity of the electrode 31 as ions. Then, cations contained in the cleaning liquid 9 are deposited on the surface of the electrode 31. The X-ray source 24 irradiates the concentrated sample near the electrode 31 with the X-ray L1 and irradiates the stirrer 90 with the X-ray L1. The stirrer 90 emits fluorescent X-rays L3 based on the X-rays L1. As a result, the concentrated sample near the electrode 31 emits the fluorescent X-ray L2 based on the X-ray L1 and the fluorescent X-ray L3. The detection unit 25 detects this fluorescent X-ray L2. The measuring unit 26 obtains the content of ions contained in the cleaning liquid 9 based on the fluorescent X-ray L2 detected by the detecting unit 25. When the valve 27 is opened, the cleaning liquid 9 in the deposition part 30 is discharged. The control unit 28 controls operations of the valve 21, the voltage generation unit 23, the X-ray source 24, and the valve 27.

(Detailed operation of the analyzer 20)
The control unit 28 opens the valve 21 at a rate of once every 10 minutes, for example. Thereby, the analyzer 20 samples the cleaning liquid 9 to be analyzed, and the pump 22 sends the sampled cleaning liquid 9 to the precipitation unit 30. Then, the control unit 28 controls the operation of the voltage generation unit 23. The voltage generation unit 23 applies a negative voltage to the electrode 31 and a positive voltage to the electrode 32 with reference to the potential of the reference electrode 33. Apply. Thereby, cations contained in the cleaning liquid 9 are concentrated near the electrode 31.

  FIG. 4 schematically shows one operation state of the precipitation unit 30. In the vicinity of the electrode 31, cations contained in the cleaning liquid 9 are attracted, and ions are deposited on the surface of the electrode 31 to form a precipitate 9 </ b> A. In this figure, illustration of ions attracted to the electrode 31 is omitted. In this figure, the amount of the precipitate 9A is exaggerated. At that time, the stirrer 90 agitates the cleaning liquid 9 in the precipitation portion 30 by rotating in the XY plane on the mesh portion 37 based on the magnetic field generated by the stirring portion 38. Thereby, in the precipitation part 30, since many ions contained in the washing | cleaning liquid 9 can be supplied near the surface of the electrode 31, many ions can be deposited in a short time.

  Next, the control unit 28 controls the X-ray source 24 after a predetermined time has elapsed after sampling the cleaning liquid 9, and the X-ray source 24 emits the X-ray L1. In this example, the X-ray L11 of the X-rays L1 excites atoms contained in the concentrated sample near the electrode 31 and emits fluorescent X-rays L2. Further, the X-ray L12 of the X-rays L1 excites atoms included in the target 92 of the stirrer 90 and emits fluorescent X-rays L3. The fluorescent X-ray L3 excites atoms contained in the concentrated sample near the electrode 31 and emits the fluorescent X-ray L2.

  In this way, the concentrated sample in the vicinity of the electrode 31 emits the fluorescent X-ray L2 based on the X-ray L1 (X-ray L11) and the fluorescent X-ray L3. The detection unit 25 detects the fluorescent X-ray L2 emitted in this way. Then, the measurement unit 26 calculates the content of ions contained in the cleaning liquid 9 based on the fluorescent X-ray L2 detected by the detection unit 25.

  Thus, in the analyzer 20, the stirrer 90 is configured using the target 92. Thereby, first, since the stirring bar 90 stirs the washing | cleaning liquid 9, many ions can be deposited in a short time. Then, when detecting the fluorescent X-ray L2, the atoms contained in the concentrated sample are excited based on the fluorescent X-ray L3 emitted from the stirrer 90 in addition to the X-ray L1 (X-ray L11). Can do. As a result, in the analyzer 20, the intensity of the fluorescent X-ray L2 can be increased, and the analysis accuracy can be increased.

  That is, for example, in the technique described in Patent Document 1, since X-rays are emitted by irradiating oil as a measurement sample with X-rays, the intensity of the fluorescent X-rays may be weakened. . On the other hand, in the analyzer 20, while the cleaning liquid 9 is being stirred using the stirrer 90, ions contained in the cleaning liquid 9 are precipitated, and the precipitate is irradiated with X-rays L <b> 1. Thereby, in the analyzer 20, since many ions can be collected in the vicinity of the electrode 31, the intensity | strength of the fluorescent X ray L2 can be raised and analysis accuracy can be raised. Furthermore, in the analyzer 20, since the stirrer 90 is configured using the target 92, it is not necessary to provide the target as a separate body. Therefore, the configuration is simplified compared to the case where the target and the stirrer are separately provided. be able to.

  In the analyzer 20, the stirrer 90, the electrode 32, and the reference electrode 33 are arranged outside the detection range R <b> 2 of the detection unit 25. Specifically, for example, the stirrer 90 is disposed on the mesh part 37, so that the stirrer 90 is disposed at a position away from the electrode 31. Thereby, in the analyzer 20, the detection unit 25 may reduce the possibility of detecting scattered X-rays from the stirrer 90, the electrode 32, and the reference electrode 33 and fluorescent X-rays L3 emitted from the stirrer 90. it can. As a result, the analysis device 20 can improve the analysis accuracy.

[effect]
As described above, in this embodiment, since the cleaning liquid in the precipitation part is stirred using the stirrer, a large number of ions can be deposited in a short time. As described above, since the amount of ions to be deposited can be increased, the analysis accuracy in the fluorescent X-ray analysis can be increased, and the analysis can be performed in a short time.

  In this embodiment, since the target is used, the atoms contained in the concentrated sample can be excited based on the X-ray emitted from the X-ray source and the fluorescent X-ray emitted from the target. Therefore, the analysis accuracy can be increased. Furthermore, in this Embodiment, since the stirring bar was comprised using the target, a structure can be simplified.

  In the present embodiment, since the stirrer, the electrode, and the reference electrode are arranged outside the detection range of the detection unit, the possibility of detecting scattered X-rays and fluorescent X-rays emitted from the stirrer is reduced. Therefore, the analysis accuracy can be increased.

[Modification 1-1]
In the above embodiment, as shown in FIG. 2, the stirrer 90, the electrode 32, and the reference electrode 33 are disposed outside the detection range R2 of the detection unit 25. However, the present invention is not limited to this. Instead of this, the stirrer 90 may be disposed within the detection range R2 of the detection unit 25 as in the precipitation unit 30A shown in FIG. Even in this case, the measurement unit 26 can distinguish between the fluorescent X-ray L2 and the fluorescent X-ray L3 by utilizing the fact that the energy of the fluorescent X-ray L2 and the energy of the fluorescent X-ray L3 are different from each other. The intensity of the X-ray L2 can be detected.

[Modification 1-2]
In the above embodiment, the cleaning liquid 9 is stirred using the stirrer 90. However, the present invention is not limited to this, and any type may be used as long as the cleaning liquid 9 is stirred. Hereinafter, this modification will be described with some examples.

  FIG. 6 illustrates a configuration example of the precipitation unit 30B according to this modification. The precipitation part 30B has a blade part 94 and a stirring part 38B. The blade part 94 agitates the cleaning liquid 9 in the precipitation part 30B by rotating in the XY plane with the shaft part 95 as a rotation axis. The blade portion 94 is connected to the stirring portion 38B via the shaft portion 95, and is rotated by the power supplied from the stirring portion 38B. Moreover, the blade | wing part 94 also has the function to radiate | emit the fluorescent X-ray L3 based on the X-ray L1, similarly to the stirring bar 90 which concerns on the said embodiment. As with the stirrer 90, the blade portion 94 is preferably coated with resin. The stirring unit 38B is configured using, for example, a motor, and rotates the blade portion 94 in the XY plane with the shaft portion 95 as a rotation axis. Even if comprised in this way, the effect similar to the case of the said embodiment can be acquired.

  FIG. 7A shows a configuration example of the precipitation unit 30C according to this modification. FIG. 7B shows a partial cross-sectional view of the inside of the precipitation portion 30C. The precipitation part 30 </ b> C has a support part 39. The support portion 39 supports the stirrer 90 so that the stirrer 90 can rotate in the XY plane. In this example, the support part 39 has a ring shape as shown in FIG. 7B. And the recessed part is formed along the circumferential direction inside the ring of the support part 39, and, thereby, the stirring element 90 is supported. In this example, the support portion 39 supports the bar-shaped stirrer 90, but is not limited thereto, and instead of this, for example, a disk-shaped stirrer may be supported. Good.

[Modification 1-3]
In the above embodiment, the analyzer 20 is applied to the cleaning device 1 and ions contained in the cleaning liquid 9 are detected. However, the present invention is not limited to this, and various applications that require detection of a very small amount of ions. Can be applied. Specifically, for example, ions contained in an etching solution used when etching is performed in a semiconductor manufacturing process may be detected.

[Modification 1-4]
In the above embodiment, the analyzer 20 is used to perform process management by detecting ions assumed in advance. However, the present invention is not limited to this, and by detecting various ions that become impurities. It may be used to manage contamination.

[Other variations]
Further, two or more of these modifications may be combined.

<2. Second Embodiment>
Next, the cleaning device 2 according to the second embodiment will be described. In the present embodiment, the method of incidence of X-rays L1 on the precipitation part is different from that of the first embodiment. In addition, the same code | symbol is attached | subjected to the substantially same component as the washing | cleaning apparatus 1 which concerns on the said 1st Embodiment, and description is abbreviate | omitted suitably.

  As shown in FIG. 1, the cleaning device 2 includes an analysis device 40. The analyzer 40 has a precipitation part 50.

  FIG. 8 illustrates a configuration example of the precipitation unit 50. The precipitation part 50 has a transmission part 51. The transmission part 51 has a property of transmitting X-rays. In this example, the transmission part 51 is provided at a position corresponding to the net part 37 on the side wall part of the container 54 of the precipitation part 50. In this example, the X-ray source 24 is provided at a position corresponding to the transmission part 51. With this configuration, the precipitation unit 50 irradiates the stirrer 90 with the X-ray L1 from the slanting direction through the transmission unit 51 and does not irradiate the electrode 31 with the X-ray L1. ing. Thereby, in the precipitation part 50, the volume of the cleaning liquid 9 in the emission range R1 of the X-ray L1 is reduced. In this example, in the precipitation unit 50, the emission range R1 of the X-ray L1 from the X-ray source 24 and the detection range R2 from the detection unit 25 are not overlapped with each other.

  FIG. 9 schematically shows one operation state of the precipitation unit 50. The X-ray L1 excites atoms contained in the target 92 of the stirrer 90 and emits fluorescent X-rays L3. This fluorescent X-ray L3 excites atoms contained in the concentrated sample (precipitate 9A in this figure). As described above, in the analyzer 40, unlike the analyzer 20 according to the first embodiment, the X-ray L1 does not directly excite atoms contained in the concentrated sample, but passes through the fluorescent X-ray L3. Indirect excitation. The detection unit 25 detects the fluorescent X-ray L2 emitted by the atoms.

  At that time, in the analyzer 40, the X-ray source 24 mainly irradiates the stirrer 90 with X-rays L <b> 1 through the transmission unit 51. Thereby, in the analyzer 40, the volume of the cleaning liquid 9 in the injection range R1 can be reduced. As a result, the analyzer 40 can suppress the influence of scattered X-rays and increase the analysis accuracy, as will be described below.

  FIG. 10 shows an X-ray spectrum. The horizontal axis indicates energy, and the vertical axis indicates X-ray intensity. A spectrum W1 represents an X-ray spectrum emitted from the X-ray source 24, and a spectrum W2 represents an X-ray spectrum detected by the detection unit 25. The X-ray spectrum W1 emitted from the X-ray source 24 includes a line spectrum W11 and a continuous spectrum W12. Similarly, the X-ray spectrum W2 detected by the detection unit 25 includes a line spectrum W21 and a continuous spectrum W22.

  The X-ray L1 corresponds to the line spectrum W11 of the X-ray spectrum W1 emitted from the X-ray source 24. This X-ray L1 excites atoms contained in the target 92 of the stirrer 90, for example, and emits fluorescent X-rays L3. The fluorescent X-ray L3 excites atoms contained in the concentrated sample and emits the fluorescent X-ray L2. Then, the detection unit 25 detects this fluorescent X-ray L2. The fluorescent X-ray L2 corresponds to the line spectrum W21 in the X-ray spectrum W2 detected by the detection unit 25. In FIG. 10, a plurality of line spectra W21 are drawn corresponding to a plurality of state transitions from the excited state.

  Further, X-rays corresponding to the continuous spectrum W12 of the X-ray spectrum W1 emitted from the X-ray source 24 are scattered by, for example, the cleaning liquid 9 or the like. And the detection part 25 detects this scattered X ray. The scattered X-rays correspond to the continuous spectrum W22 in the X-ray spectrum W2 detected by the detection unit 25.

  As described above, the X-ray spectrum W2 detected by the detection unit 25 includes a continuous spectrum W22 related to scattered X-rays. When the X-ray intensity of the continuous spectrum W22 is strong, the line spectrum W21 related to the fluorescent X-ray L2 may be buried. In such a case, the detection accuracy of the ion content in the cleaning liquid 9 may be reduced.

  On the other hand, in the analyzer 40, the volume of the cleaning liquid 9 in the injection range R1 is reduced by irradiating the stirrer 90 mainly with the X-ray L1 through the transmission part 51. In particular, in the analyzing apparatus 40, in the precipitation unit 50, the emission range R1 (a space region where the X-ray L1 travels) and the detection range R2 (a detectable space region) are prevented from overlapping each other. Thereby, in the analyzer 40, since the possibility that the X-ray emitted from the X-ray source 24 is scattered by the cleaning liquid 9 can be reduced, the X-ray intensity of the continuous spectrum W22 related to the scattered X-ray can be lowered. . As a result, in the analyzer 40, the detection accuracy of the ion content in the cleaning liquid 9 can be increased, and the analysis accuracy can be increased.

  As described above, in this embodiment, the stirrer is mainly irradiated with X-rays through the transmission part. In particular, in the present embodiment, the injection range and the detection range are not overlapped with each other in the precipitation portion. Thereby, since the possibility that the X-rays emitted from the X-ray source are scattered by the cleaning liquid can be reduced, the analysis accuracy can be increased. Other effects are the same as in the case of the first embodiment.

  Although the present invention has been described with reference to some embodiments and modifications, the present invention is not limited to these embodiments and the like, and various modifications can be made.

  For example, in each of the above-described embodiments, the reference electrode 33 is provided. However, the present invention is not limited to this, and the reference electrode may be omitted.

  Further, for example, in each of the above-described embodiments and the like, analysis was performed without flowing the sampled cleaning liquid 9, but the present invention is not limited to this. Instead of this, for example, the sampled cleaning liquid 9 may be analyzed while flowing from the inlet 35 to the outlet 36 of the precipitation units 30 and 50.

In addition, this invention can be set as the following structures.
(1) a container for storing a liquid sample;
An electrode provided in the container;
An X-ray source emitting primary X-rays;
A stirrer that emits secondary X-rays based on the primary X-rays and stirs the liquid sample;
A liquid sample analyzer comprising: a detection unit configured to detect fluorescent X-rays emitted from a concentrated sample concentrated in the vicinity of the electrode from the liquid sample based on the secondary X-ray.
(2) The liquid sample analyzer according to (1), wherein the stirring member includes an element having an atomic number larger than an atomic number of an analysis target ion included in the liquid sample.
(3) The liquid sample analyzer according to (1) or (2), wherein the X-ray source is arranged so that the stirring member and the electrode are included in a space region where the primary X-rays travel.
(4) In the X-ray source, the stirring member is included in a space region where the primary X-rays travel, and the electrode is included in a space region other than the space region where the primary X-rays travel. The liquid sample analyzer according to (1) or (2), which is arranged.
(5) The liquid sample analyzer according to (4), wherein a space region in which the primary X-rays travel and a detectable space region of the detection unit do not overlap each other in the container.
(6) The liquid sample analyzer according to any one of (1) to (5), wherein the stirring member is disposed apart from the electrode.
(7) The liquid sample analyzer according to any one of (1) to (6), wherein the stirring member is disposed outside a detectable space region of the detection unit.
(8) The liquid sample analyzer according to any one of (1) to (7), wherein the stirring member includes a magnetic body.
(9) The liquid sample according to any one of (1) to (8), wherein the concentrated sample includes a precipitate of ions to be analyzed included in the liquid sample, which is deposited on a surface of the electrode. Analysis equipment.

  DESCRIPTION OF SYMBOLS 1, 2 ... Cleaning apparatus, 8 ... Flow path, 9 ... Cleaning liquid, 9A ... Precipitate, 11 ... Cleaning part, 12 ... Pump, 13 ... Filter, 20, 40 ... Analysis apparatus, 21 ... Valve, 22 ... Pump, 23 DESCRIPTION OF SYMBOLS ... Voltage generation part, 24 ... X-ray source, 25 ... Detection part, 26 ... Measurement part, 27 ... Valve, 28 ... Control part, 30, 30A, 30B, 30C, 50 ... Deposition part, 31, 32 ... Electrode, 33 Reference electrode, 34, 54 ... Container, 35 ... Inlet port, 36 ... Outlet port, 37 ... Net part, 38 ... Stirrer part, 39 ... Support part, 51 ... Permeator part, 90 ... Stirrer, 91 ... Magnet, 92 ... target, 93 ... coating, 94 ... blade, 95 ... shaft, L1 ... X-ray, L2, L3 ... fluorescent X-ray, R1 ... emission range, R2 ... detection range, W1, W2 ... spectrum, W11, W21 ... Line spectrum, W12, W22 ... continuous spectrum.

Claims (9)

A container containing a liquid sample;
An electrode provided in the container;
An X-ray source emitting primary X-rays;
A stirrer that emits secondary X-rays based on the primary X-rays and stirs the liquid sample;
A liquid sample analyzer comprising: a detection unit configured to detect fluorescent X-rays emitted from a concentrated sample concentrated in the vicinity of the electrode from the liquid sample based on the secondary X-ray. The liquid sample analyzer according to claim 1, wherein the stirring member includes an element having an atomic number larger than an atomic number of an analysis target ion included in the liquid sample. The liquid sample analyzer according to claim 1, wherein the X-ray source is arranged so that the stirring member and the electrode are included in a space region where the primary X-rays travel. The X-ray source is arranged so that the stirring member is included in a space region where the primary X-rays travel, and the electrode is included in a space region other than the space region where the primary X-rays travel The liquid sample analyzer according to claim 1 or 2. The liquid sample analyzer according to claim 4, wherein a spatial region in which the primary X-ray travels and a detectable spatial region of the detection unit do not overlap each other in the container. The liquid sample analyzer according to any one of claims 1 to 5, wherein the stirring member is disposed apart from the electrode. The liquid sample analyzer according to claim 1, wherein the stirring member is disposed outside a detectable space area of the detection unit. The liquid sample analyzer according to any one of claims 1 to 7, wherein the stirring member includes a magnetic body. The liquid sample analyzer according to any one of claims 1 to 8, wherein the concentrated sample includes a precipitate of ions to be analyzed included in the liquid sample, which is deposited on a surface of the electrode.

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