JP2017083345A - 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 flow path having a narrow part, in which a liquid sample flows; an electrode in the narrow part; an X-ray source emitting X-rays to the electrode; and a detection unit that detects a fluorescent X-ray emitted from a concentrated sample of the liquid sample near the electrode, based on the 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 detects ions contained in a liquid sample using fluorescent X-rays while flowing the liquid sample.

  By the way, when analyzing a substance, a diffracted X-ray may be used. For example, Patent Document 2 discloses an analyzer that measures the structure of a precipitate using diffraction X-rays while flowing an electrolytic solution. In this analyzer, the thickness of the electrolyte layer between the carbon plate window and the sample electrode is controlled so that the electrolyte flows stably and the diffracted X-rays are not attenuated.

JP 2005-172719 A JP-A-9-279400

  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 first liquid sample analyzer of the present invention includes a flow path, an electrode, an X-ray source, and a detection unit. The flow channel is a channel through which a liquid sample flows and has a constriction. The electrode is disposed in the constriction. The X-ray source emits X-rays toward the electrodes. 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 X-rays.

  The second liquid sample analyzer of the present invention includes a flow path, an electrode, an X-ray source, and a detection unit. The flow path is where the liquid sample flows. The electrode constitutes a channel wall of the channel. The X-ray source is configured such that X-rays are emitted toward the electrode, and the incident angle of the X-rays with respect to the inner surface of the flow path wall is an angle at which the X-rays are totally reflected. 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 X-rays.

  According to the first liquid sample analyzer of the present invention, since the narrowed portion is provided, the analysis accuracy can be improved.

  According to the second liquid sample analyzer of the present invention, the X-ray incident angle with respect to the inner surface of the flow path wall is set to an angle at which the X-ray is totally reflected, so that the analysis accuracy can be improved.

It is a block diagram showing the example of 1 structure of the washing | cleaning apparatus which concerns on the 1st Embodiment of this invention. It is sectional drawing showing the example of 1 structure of the precipitation part shown in FIG. FIG. 3 is a schematic diagram illustrating an operation example of the analysis apparatus illustrated in FIG. 1. It is explanatory drawing showing a spectrum. It is a schematic diagram showing the operation example of the analyzer which concerns on a modification. It is a schematic diagram showing the operation example of the analyzer 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 block diagram showing the example of 1 structure of the washing | cleaning apparatus which concerns on another modification. It is a block diagram showing the example of 1 structure of the washing | cleaning apparatus which concerns on 2nd Embodiment. It is sectional drawing showing the example of 1 structure of the precipitation part shown in FIG. It is a top view showing one structural example of the precipitation part shown in FIG. FIG. 9 is a schematic diagram illustrating an operation example of the analysis apparatus illustrated in FIG. 8. It is a schematic diagram showing the operation example of the analyzer which concerns on a modification. It is a schematic diagram showing the operation example of the analyzer which concerns on a modification. It is a schematic diagram showing the operation example of the analyzer which concerns on another modification. It is a schematic diagram showing the operation example of the analyzer which concerns on another modification.

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 analysis device 20 detects the amount of ions contained in the cleaning liquid 9 using fluorescent X-rays, and is a so-called flow cell type device. The analyzer 20 includes a valve 21, a deposition unit 30, a voltage generation unit 22, an X-ray source 23, a detection unit 24, a measurement unit 25, a pump 26, valves 27 and 29, and a control unit 28. have. The valve 21, the precipitation unit 30, the pump 26, and the valves 27 and 29 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 precipitation part 30 precipitates ions contained in the cleaning liquid 9 flowing from the inlet 35 toward the outlet 36.

  FIG. 2 shows a configuration example of the precipitation unit 30. In FIG. 2, in addition to the precipitation unit 30, a voltage generation unit 22, an X-ray source 23, and a detection unit 24 are also drawn for convenience of explanation. The deposition part 30 has a constriction part 39, electrodes 31 and 32, and a reference electrode 33.

  The narrowed portion 39 is a portion where the channel width of the channel 8 is narrowed. In this example, the narrowed portion 39 is configured such that the flow path width in the normal direction of the electrode 31 is narrowed. Thereby, in the constriction part 39, the flow-path cross-sectional area in the flow path 8 is small.

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. The electrode 31 is provided at a position corresponding to the narrowed portion 39. In this example, the electrode 31 is provided so as to cover an opening provided in the wall of the flow path 8 and constitutes a part of the wall of the flow path 8. As will be described later, a negative voltage is applied to the electrode 31 by the voltage generator 22. 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 23, as will be described later. As a result, the X-ray L1 passes through the electrode 31 and irradiates the concentrated sample in the vicinity of the electrode 31. 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. The electrode 32 and the reference electrode 33 are provided at a position away from the narrowed portion 39 so that the X-ray L1 is not irradiated. In this example, the reference electrode 33 is provided, but this may be omitted.

  The voltage generation unit 22 (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 22 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 22 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 23 emits X-rays L <b> 1 to the concentrated sample near the electrode 31. The X-ray source 23 operates based on a control signal supplied from the control unit 28. In this example, the X-ray source 23 is arranged on the side (lower side in FIG. 2) where the electrode 31 is arranged as viewed from the flow path 8. In other words, the X-ray source 23 is arranged so that the X-ray L1 passes through the electrode 31 and is irradiated to the concentrated sample in the vicinity of the electrode 31. Thereby, in the analyzer 20, since the X-ray L1 does not advance through the cleaning liquid 9, the possibility that the X-ray L1 is attenuated can be reduced.

  The detection unit 24 detects fluorescent X-rays L2 emitted from the concentrated sample in the vicinity of the electrode 31, and is configured using, for example, a semiconductor detector or a silicon drift detector (SDD). In this example, the detection unit 24 is arranged on the side (the lower side in FIG. 2) where the electrode 31 is arranged as viewed from the flow path 8. In other words, the detection unit 24 is arranged so that the fluorescent X-rays L2 emitted from the concentrated sample near the electrode 31 pass through the electrode 31 and enter the detection unit 24. Thereby, in the analyzer 20, since the fluorescent X-rays L2 do not travel through the cleaning liquid 9, the possibility that the fluorescent X-rays L2 are attenuated can be reduced.

  The measurement unit 25 obtains the content of ions contained in the cleaning liquid 9 based on the fluorescent X-ray L2 detected by the detection unit 24. The measurement unit 25 includes, for example, an amplifier, a pulse height analyzer, a multichannel analyzer, and the like. With this configuration, the measurement unit 25 specifies the element that emits the fluorescent X-ray L2 based on the energy of the fluorescent X-ray L2, and obtains the ion content based on the intensity of the fluorescent X-ray L2. It has become. Moreover, the measurement part 25 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 pump 26 circulates the cleaning liquid 9 by sending the cleaning liquid 9 flowing out from the outlet 36 of the precipitation unit 30 to the introduction port 35 of the precipitation unit 30. The valve 27 is provided on the flow path 8 from the pump 26 to the introduction port 35 of the deposition part 30. The valve 29 is for discharging the cleaning liquid 9 circulating through the precipitation part 30, the pump 26, and the valve 27 from the flow path 8 between the pump 26 and the valve 27. Opening and closing of the valves 27 and 29 is controlled by the control unit 28. The control unit 28 controls operations of the valve 21, the voltage generation unit 22, the X-ray source 23, and the valves 27 and 29.

  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.

[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 26 causes the cleaning liquid 9 to flow from the inlet 35 to the outlet 36 of the precipitation unit 30 by circulating the cleaning liquid 9. For example, the voltage generation unit 22 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, 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 23 irradiates the concentrated sample near the electrode 31 with X-rays L1. Thereby, the concentrated sample emits fluorescent X-rays L2 based on the X-rays L1. The detection unit 24 detects this fluorescent X-ray L2. The measurement unit 25 obtains the content of ions contained in the cleaning liquid 9 based on the fluorescent X-ray L2 detected by the detection unit 24. When the valve 29 is in the open state, the cleaning liquid 9 circulating through the precipitation unit 30 and the pump 26 is discharged. The control unit 28 controls operations of the valve 21, the voltage generation unit 22, the X-ray source 23, and the valves 27 and 29.

(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. Specifically, first, the control unit 28 opens the valves 21 and 29 and closes the valve 27 to operate the pump 26. As a result, the cleaning liquid 9 flows in the order of the valve 21, the precipitation unit 30, the pump 26, and the valve 29, and the flow path 8 passing through these flows is filled with the cleaning liquid 9. Then, the control unit 28 opens the valve 27. Accordingly, the cleaning liquid 9 further flows in the order of the valve 21, the valve 27, and the valve 29, and the flow path 8 around the valve 27 is filled with the cleaning liquid 9. Thereafter, the control unit 28 closes the valves 21 and 29. The cleaning liquid 9 sampled in this way circulates in the order of the pump 26, the valve 27, and the deposition unit 30.

  In the precipitation unit 30, the cleaning liquid 9 flows from the inlet 35 toward the outlet 36. The control unit 28 controls the operation of the voltage generation unit 22, and the voltage generation unit 22 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, cations contained in the cleaning liquid 9 are concentrated near the electrode 31.

  FIG. 3 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, since the flow path width is narrow in the narrowed portion 39, the flow rate of the cleaning liquid 9 is increased. 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 23 after a predetermined time has elapsed after sampling the cleaning liquid 9, and the X-ray source 23 emits the X-ray L1. As shown in FIG. 3, the X-ray L1 excites atoms contained in the concentrated sample near the electrode 31, and emits fluorescent X-rays L2. The detection unit 24 detects the fluorescent X-ray L2 emitted in this way. Then, the measurement unit 25 calculates the content of ions contained in the cleaning liquid 9 based on the fluorescent X-ray L2 detected by the detection unit 24.

  At that time, since the narrowed portion 39 is provided in the analyzer 20, as described below, the detection accuracy of the ion content contained in the cleaning liquid 9 can be improved by suppressing the influence of scattered X-rays. Can do.

  FIG. 4 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 23, and a spectrum W2 represents an X-ray spectrum detected by the detection unit 24. The X-ray spectrum W1 emitted from the X-ray source 23 includes a line spectrum W11 and a continuous spectrum W12. Similarly, the X-ray spectrum W2 detected by the detection unit 24 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 23. This X-ray L1 excites atoms contained in the concentrated sample and emits fluorescent X-rays L2. Then, the detection unit 24 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 24. In FIG. 4, 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 23 are scattered by, for example, the cleaning liquid 9, the precipitate 9A, the electrode 31, and the like. And the detection part 24 also 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 24.

  As described above, the X-ray spectrum W2 detected by the detection unit 24 includes the continuous spectrum W22 related to the 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 20, since the narrowed portion 39 is provided and the flow path width of the flow path 8 is narrowed, the volume of the cleaning liquid 9 in the X-ray emission range emitted from the X-ray source 23 can be reduced. it can. Thereby, in the analyzer 20, since the possibility that the X-rays emitted from the X-ray source 23 are scattered by the cleaning liquid 9 can be reduced, the X-ray intensity of the continuous spectrum W22 related to the scattered X-rays can be lowered. . As a result, the analyzer 20 can improve the detection accuracy of the ion content in the cleaning liquid 9.

[effect]
As described above, in the present embodiment, the constriction is provided and the flow rate of the cleaning liquid is increased, so that more ions can be supplied near the surface of the electrode 31, so that more ions can be supplied in a short time. It can be deposited. 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 constriction is provided and the volume of the cleaning liquid in the X-ray emission range is reduced, the possibility that the X-rays are scattered by the cleaning liquid can be reduced, so that the detection accuracy is improved. Can do.

[Modification 1-1]
In the above-described embodiment, the X-ray source 23 and the detection unit 24 are disposed on the side (the lower side in FIG. 2) where the electrode 31 is disposed as viewed from the flow path 8, but the present invention is not limited to this. For example, like the precipitation part 30A shown in FIG. 5A, the detection part 24 may be arranged on the side opposite to the side where the electrode 31 is arranged (upper side in FIG. 5A). In this example, the detection unit 24 is arranged so that the fluorescent X-ray L2 enters the detection unit 24 across the cleaning liquid 9 in the flow path 8. Moreover, you may arrange | position the X-ray source 23 on the opposite side (upper side in FIG. 5B) to the side where the electrode 31 is arrange | positioned like the precipitation part 30B shown to FIG. 5B. In this example, the X-ray source 23 is arranged so that the X-ray L1 is irradiated to the precipitate 9A across the cleaning liquid 9 in the flow path 8. Moreover, you may arrange | position both the X-ray source 23 and the detection part 24 on the opposite side to the side in which the electrode 31 is arrange | positioned.

[Modification 1-2]
In the above embodiment, the narrowed portion 39 is configured by narrowing a part of the flow path 8 that goes straight, but the present invention is not limited to this. For example, a constricted portion may be configured by narrowing a part of the bent flow path 8 like a precipitation portion 30C shown in FIG. The deposition part 30C has a constriction part 39C, electrodes 31C and 32C, and a reference electrode 33C. In this example, the flow path 8 in the precipitation part 30C has a substantially U shape, and the cleaning liquid 9 flows from the inlet 35C toward the outlet 36C.

[Modification 1-3]
In the above embodiment, a part of the cleaning liquid 9 circulating through the cleaning unit 11, the pump 12, and the filter 13 is sampled, and the amount of ions contained in the sampled cleaning liquid 9 is detected. However, the present invention is not limited to this. is not. For example, the amount of ions contained in the cleaning liquid 9 can be detected by circulating the cleaning liquid 9 through the cleaning unit 11, the precipitation unit 30, the pump 12, and the filter 13 as in the cleaning apparatus 1D shown in FIG. Good. The cleaning apparatus 1D includes a cleaning unit 11, a deposition unit 30, a voltage generation unit 22, an X-ray source 23, a detection unit 24, a measurement unit 25, a pump 12, a filter 13, and a control unit 28D. I have. In this example, the cleaning liquid 9 used for cleaning discharged from the cleaning unit 11 is supplied to the inlet 35 of the deposition unit 30. The pump 12 sends the cleaning liquid 9 flowing out from the outlet 36 of the precipitation unit 30 to the filter 13. The control unit 28D controls the operation of the voltage generation unit 22 and the X-ray source 23. With this configuration, the cleaning apparatus 1D can determine the content of ions contained in the cleaning liquid 9 without performing sampling. In this configuration, for example, a part of the components of the electrode 31 in the precipitation part 30 may be dissolved in the cleaning liquid 9. Therefore, this configuration can be applied to an application in which such a phenomenon does not cause a problem.

[Modification 1-4]
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 1-5]
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.

  FIG. 8 illustrates a configuration example of the cleaning apparatus 2 according to the present embodiment. The cleaning device 2 includes an analysis device 40. The analysis device 40 includes a precipitation unit 50 and a collimator 43.

  9A and 9B show a configuration example of the precipitation unit 50. FIG. 9A shows a cross-sectional view in the direction of arrows II along the two-dot chain line in FIG. 9B. As shown in FIG. 9A, the flow path 8 in the precipitation part 50 has a substantially U shape, and the cleaning liquid 9 flows from the inlet 55 toward the outlet 56. In this example, the flow path 8 related to the inlet 55 and the flow path 8 related to the outlet 56 are arranged so as to extend in the Z direction. Further, the flow path 8 related to the inlet 55 and the flow path 8 related to the outlet 56 are arranged at positions shifted from each other in the Y direction as shown in FIG. 9B.

  The deposition part 50 includes a constriction part 59, electrodes 51 and 52, and a reference electrode 53. The narrowed portion 59, the electrodes 51, 52, and the reference electrode 53 correspond to the narrowed portion 39, the electrodes 31, 32, and the reference electrode 33 according to the first embodiment, respectively. In the constricted portion 59, the cleaning liquid 9 flows in the Y direction as shown in FIG. 9B.

  The collimator 43 (FIG. 8) aligns the traveling direction of the X-rays L1 emitted from the X-ray source 23, and is configured using, for example, a slit.

  In this example, the X-ray source 23 is disposed at such a position that the X-ray L1 is irradiated to the concentrated sample in the vicinity of the electrode 51 across the cleaning liquid 9 in the flow path 8 in the constriction 59. At that time, as shown in FIGS. 9A and 9B, the X-ray L1 proceeds without crossing the flow path 8 related to the introduction port 55 and reaches the constricted portion 59. The X-ray L1 is totally reflected at the interface between the cleaning liquid 9 and the electrode 51 in the narrowed portion 59. Further, in this example, the detection unit 24 is arranged at a position where the fluorescent X-ray L2 passes through the electrode 51 and enters the detection unit 24.

  Here, the analyzer 40 corresponds to a specific example of “liquid sample analyzer” in the present invention. The electrode 51 corresponds to a specific example of “electrode” in the present invention.

  FIG. 10 shows a state in which the precipitate is irradiated with the X-ray L1. The incident angle θ of the X-ray L1 with respect to the surface of the electrode 51 is an angle that satisfies the total reflection condition. For example, when the energy of the X-ray L1 is 20 keV and the electrode 51 is made of carbon, the total reflection critical angle should be 0.078 degrees in order to satisfy such a total reflection condition. it can. In this case, the incident angle θ can be, for example, 89.922 (= 90−0.078) degrees or more. In other words, the visual oblique angle can be set to 0.078 degrees or less.

  The X-ray L11 of the X-rays L1 excites atoms contained in the concentrated sample near the electrode 51 and emits fluorescent X-rays L2 as in the case of the first embodiment. Then, the detection unit 24 detects this fluorescent X-ray L2. On the other hand, the X-ray L12 of the X-rays L1 passes through the precipitate 9A and reaches the interface between the cleaning liquid 9 (precipitate 9A) and the electrode 51 in this example. The X-ray L12 is totally reflected at this interface.

  Thus, in the analyzer 40, the X-ray L1 (X-ray L12) that reached the interface between the cleaning liquid 9 (precipitate 9A) and the electrode 51 was totally reflected on the surface of the electrode 51. Thereby, in the precipitation part 50, since X-ray L1 does not penetrate | invade in the electrode 51, a possibility that X-ray L1 may be scattered in the electrode 51 can be reduced, and it is the same as the case of 1st Embodiment. The X-ray intensity of the continuous spectrum W22 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, since the X-ray L1 is totally reflected on the surface of the electrode 51, the possibility that the X-ray L1 is scattered in the electrode 51 can be reduced. Can be increased. Other effects are the same as in the case of the first embodiment.

[Modification 2-1]
In the said embodiment, although the shape of the flow path 8 in the precipitation part 50 was made into the substantially U shape, it is not limited to this. For example, as shown in FIGS. 11A and 11B, a precipitation portion 50A having the same configuration as the precipitation portion 30 according to the first embodiment may be used. FIG. 11A shows a cross-sectional configuration of the precipitation portion 50A in the XZ plane, and FIG. 11B shows a cross-sectional configuration of the constriction portion 39 in the YZ plane. In this example, as shown in FIG. 11A, the precipitation portion 50A is arranged so that the flow path 8 extends in the X direction. Then, as shown in FIG. 11B, the X-ray source 23 and the collimator 43 are arranged in the YZ plane. At this time, the X-ray L1 is totally reflected at the interface between the cleaning liquid 9 and the electrode 31 in the narrowed portion 39. Moreover, as shown in FIG. 12, while using the precipitation part 50B which has the structure similar to the precipitation part 30 which concerns on 1st Embodiment, even if it arrange | positions the X-ray source 23 and the collimator 43 in XZ plane Good.

[Modification 2-2]
In the said embodiment, although the precipitation part 50 which has the constriction part 59 was used, it is not limited to this. Instead, for example, as illustrated in FIG. 13, a precipitation portion 50 </ b> C that does not have a constriction portion may be used. The precipitation portion 50C is configured such that the constriction portion 39 is not provided in the precipitation portion 30 according to the first embodiment. In this example, the precipitation part 50C is arranged so that the flow path 8 extends in the X direction. The X-ray source 23 and the collimator 43 are arranged in the XZ plane. The X-ray L1 is totally reflected at the interface between the cleaning liquid 9 and the electrode 31 in the flow path 8.

  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 embodiments, the reference electrodes 33 and 53 are 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, the electrodes 31 and 51 constitute a part of the wall of the flow path 8, but the present invention is not limited to this. Instead of this, for example, the electrodes 31 and 51 may be disposed inside the flow path 8.

In addition, this invention can be set as the following structures.
(1) a flow path through which a liquid sample flows and having a constriction,
An electrode disposed in the constriction,
An X-ray source emitting X-rays toward the electrode;
A liquid sample analyzer comprising: a detection unit that detects fluorescent X-rays emitted from a concentrated sample concentrated in the vicinity of the electrode from the liquid sample based on the X-ray.
(2) The electrode constitutes a channel wall of the channel,
The liquid sample analyzer according to (1), wherein an inner surface of the channel wall is an incident surface of the X-ray.
(3) The liquid sample analyzer according to (2), wherein an incident angle of the X-ray with respect to an inner surface of the flow path wall is an angle at which the X-ray is totally reflected.
(4) The liquid sample analyzer according to (2) or (3), further including a collimator between the X-ray source and the electrode.
(5) The electrode constitutes a channel wall of the channel,
The liquid sample analyzer according to (1), wherein an outer surface of the channel wall is an incident surface of the X-ray.
(6) The liquid sample analyzer according to any one of (1) to (5), further including a measurement unit that measures energy and intensity of the fluorescent X-ray based on a detection result of the detection unit.
(7) The liquid sample analyzer according to any one of (1) to (6), wherein the concentrated sample includes a precipitate of ions to be analyzed included in the liquid sample deposited on the surface of the electrode. .
(8) further comprising a pump disposed on the flow path,
The liquid sample analyzer according to any one of (1) to (7), wherein the flow path is configured to allow the liquid sample to circulate.
(9) a flow path through which the liquid sample flows;
An electrode constituting a flow path wall of the flow path;
An X-ray source configured to emit X-rays toward the electrode, and an incident angle of the X-rays with respect to the inner surface of the flow path wall is an angle at which the X-rays are totally reflected;
A liquid sample analyzer comprising: a detection unit that detects fluorescent X-rays emitted from a concentrated sample concentrated in the vicinity of the electrode from the liquid sample based on the X-ray.

  DESCRIPTION OF SYMBOLS 1,1D, 2 ... Cleaning apparatus, 8 ... Flow path, 9 ... Cleaning liquid, 9A ... Precipitate, 11 ... Cleaning part, 12 ... Pump, 13 ... Filter, 20, 40 ... Analyzer, 21 ... Valve, 22 ... Voltage Generation unit, 23 ... X-ray source, 24 ... detection unit, 25 ... measurement unit, 26 ... pump, 27,29 ... valve, 28,28D ... control unit, 30, 30A-30C, 50, 50A-50C ... precipitation unit , 31, 31C, 32, 32C, 51, 52 ... electrode, 33, 33C, 53 ... reference electrode, 35, 35C, 55 ... inlet, 36, 36C, 56 ... outlet, 39, 59 ... constriction, 43 ... collimator, L1, L11, L12 ... X-ray, L2 ... fluorescent X-ray, W1, W2 ... spectrum, W11, W21 ... line spectrum, W12, W22 ... continuous spectrum, [theta] ... incident angle.

Claims (9)

A flow path through which the liquid sample flows and having a constriction,
An electrode disposed in the constriction,
An X-ray source emitting X-rays toward the electrode;
A liquid sample analyzer comprising: a detection unit that detects fluorescent X-rays emitted from a concentrated sample concentrated in the vicinity of the electrode from the liquid sample based on the X-ray. The electrode constitutes a channel wall of the channel,
The liquid sample analyzer according to claim 1, wherein an inner surface of the flow path wall is an incident surface of the X-ray. The liquid sample analyzer according to claim 2, wherein an incident angle of the X-ray with respect to an inner surface of the flow path wall is an angle at which the X-ray is totally reflected. The liquid sample analyzer according to claim 2, further comprising a collimator between the X-ray source and the electrode. The electrode constitutes a channel wall of the channel,
The liquid sample analyzer according to claim 1, wherein an outer surface of the channel wall is an incident surface of the X-ray. The liquid sample analyzer according to claim 1, further comprising a measurement unit that measures energy and intensity of the fluorescent X-ray based on a detection result of the detection unit. The liquid sample analyzer according to any one of claims 1 to 6, wherein the concentrated sample includes a deposit of ions to be analyzed included in the liquid sample deposited on a surface of the electrode. A pump disposed on the flow path;
The liquid sample analyzer according to any one of claims 1 to 7, wherein the flow path is configured to allow the liquid sample to circulate. A flow path through which a liquid sample flows;
An electrode constituting a flow path wall of the flow path;
An X-ray source configured to emit X-rays toward the electrode, and an incident angle of the X-rays with respect to the inner surface of the flow path wall is an angle at which the X-rays are totally reflected;
A liquid sample analyzer comprising: a detection unit that detects fluorescent X-rays emitted from a concentrated sample concentrated in the vicinity of the electrode from the liquid sample based on the X-ray.

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