JP2008039772A - X-ray analyzer and x-ray analysis method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To nondestructively analyze elements in a very small space inside samples. <P>SOLUTION: A primary X-ray source 1 for generating X-rays for excitation is connected to a conduit 5 for X-ray detection by an X-ray irradiation mechanism. An X-ray detector 9 is coupled with a base end part of the conduit 5 for X-ray detection so that fluorescent X-rays discharged from a sample 7 may be passed through an internal passage 4 from an opening at a tip part and guided to the X-ray detector 9. The inside of the conduit 5 for X-ray detection is provided with a secondary target 3 for receiving a primary X-ray beam incident via a conduit 2a for X-ray incidence, generating a secondary X-ray beam, and irradiating it to the sample via the tip part of the conduit 5 for X-ray detection. Since the secondary target 3 is formed in a ring shape and provided for the inside of the conduit 5 for X-ray detection and in an outer circumference of the internal passage 4 in the conduit 5 and has an inclined plane in its tip part, it is possible to efficiently irradiate the secondary X-ray beam in the direction of the sample. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an X-ray analysis method for performing elemental analysis, qualitative analysis, quantitative analysis, measurement of a chemical bonding state, and the like for a biological sample, a solid sample, a liquid sample, a solid sample in a liquid, and the like, and an apparatus used therefor.

As a method for performing elemental analysis, qualitative analysis, and quantitative analysis of the sample surface, FE-AES (in which a surface of a solid sample is irradiated with an electron beam and elemental analysis in a region several nm deep from the surface is performed by the generated secondary electrons. Field emission Auger electron spectroscopy), TOF-SIMS (time-of-flight secondary ion mass spectrometry) that irradiates a solid sample with a high-speed ion beam and performs elemental analysis of the outermost surface of the sample by sputtering, and an electron beam to the sample EPMA (X-ray microanalysis) is known which performs elemental analysis of the sample surface by irradiation and the characteristic X-rays generated.
X-ray fluorescence analysis, in which an X-ray beam is irradiated onto a measurement object, thereby detecting the fluorescent X-rays generated from the object and identifying the elements constituting the sample, is one type of surface analysis technique.

When elemental analysis inside a sample is performed by fluorescent X-ray analysis, a method is generally used in which a cross section of the sample is cut out and the surface thereof is measured, but the sample is destroyed when cut out.
As a method of nondestructive elemental analysis of the minute space inside the sample, two X-ray condenser lenses are arranged on the excitation side and the detector side, and adjusted so that the confocal point comes inside the sample, A method of performing three-dimensional X-ray fluorescence analysis in a sample has been proposed (see Non-Patent Document 1).

  In this method, an X-ray beam is irradiated from the outside of the sample, and only fluorescent X-rays excited by the X-ray and emitted from the sample to the atmosphere (or vacuum) side are detected. However, with this method, the X-ray intensity is significantly attenuated, and the penetration depth of X-rays from the sample and the detection depth of fluorescent X-rays depend on the energy of the X-rays and the type of sample, but from several μm. It will be as shallow as several millimeters.

Proceeding of SPIE 4144 (2000) 174-182

  In the above method, it is necessary to arrange the two X-ray condenser lenses so that the confocal point intersects the target part. However, it is difficult to adjust the confocal point to the target part, and the position thereof is adjusted. It is cumbersome to do.

  Therefore, an object of the present invention is to provide an X-ray analysis apparatus that can perform elemental analysis of a sample without performing complicated operations.

An X-ray analyzer of the present invention includes an X-ray irradiation mechanism that irradiates a sample with an X-ray beam from the tip, an X-ray detector that detects fluorescent X-rays emitted from the sample, and an X-ray detector at the base end. And an X-ray detection conduit that is arranged on the same side as the X-ray irradiation mechanism with respect to the sample and guides the fluorescent X-rays incident from the tip through the internal passage to the X-ray detector. The tip portion of the X-ray irradiation mechanism and the tip portion of the X-ray detection conduit are combined into one so that the sample is irradiated with an X-ray beam and fluorescent X-rays from the sample are incident.
“Arranged on the same side” means that the X-ray irradiation mechanism and the X-ray detection conduit are arranged only on the upper surface side of the sample surface, for example.

  In order to irradiate the secondary X-ray beam having a reduced background, the base end portion of the X-ray irradiation mechanism is coupled to the primary X-ray source, and the primary X-ray beam from the primary X-ray source is included in the X-ray irradiation mechanism. It is preferable that a secondary target for generating a secondary X-ray beam in response to the sample and irradiating the sample through the tip is provided.

In order to efficiently irradiate the sample with the secondary X-ray beam, the X-ray irradiation mechanism irradiates the sample with the X-ray and the X-ray detection conduit are integrated on the same axis, and the secondary target has a hole. The fluorescent X-rays provided from the sample may be guided to the X-ray detector through the hole. The position where the hole is made is, for example, the center of the secondary target, but is not limited thereto.
Here, “on the same axis” means that the optical axis of the X-ray beam applied to the sample and the optical axis of the fluorescent X-ray emitted from the sample are substantially the same, but not completely the same. Also good.

  Further, in order to reduce the size of the apparatus, a portion for irradiating the sample with X-rays by the X-ray irradiation mechanism may be arranged in the X-ray detection conduit.

  When measuring a minute part, it is preferable that the outer diameter of the conduit is small and the volume occupied by the conduit is small. Therefore, the portion where the sample is irradiated with X-rays by the X-ray irradiation mechanism is included in the X-ray detection conduit. , And the secondary target may be disposed in the X-ray irradiation conduit.

  Since a sufficient space is required to arrange an apparatus such as an X-ray source, the X-ray irradiation mechanism irradiates the sample with X-rays and the X-ray detection conduit from the combined distal end. You may arrange | position with an angle so that it may spread toward both base end parts.

  Since X-rays attenuate when a sample or the like enters the conduit, it is preferable that an X-ray permeable protective film that closes the opening is provided at the combined tip.

  The X-ray permeable protective film may be any film that can transmit X-rays, and an example thereof is a polymer film.

  A preferable example of the conduit is a collimator having a pointed tip, or an injection needle used for medical solution injection or blood collection in the medical field. As the material of the conduit, the same material as that of the secondary target is preferable because an extra impurity fluorescent X-ray peak can be suppressed. For example, when the secondary target is made of Cu, the conduit may be made of Cu.

  Moreover, when measuring by inserting in a solid sample, it is preferable to use the needle | hook with a taper (inclination) at the front-end | tip.

  Since the depth from the sample surface to the site to be measured is determined by the insertion depth of the conduit, the depth can be several mm to several centimeters from the sample surface or deeper.

  Further, since the size of the site to be measured is determined by the distance between the tips of both conduits inserted into the sample, it can be a micro site having a diameter of several mm or 1 mm or less.

  There is also a demand for elemental analysis of a minute portion such as several tens to several hundreds of μm on the sample surface. In a preferred embodiment of the present invention to meet such a demand, a combined capillary tip has a polycapillary half lens that collects an X-ray beam on a minute portion of the sample, and fluorescent X-rays from the minute portion of the sample. Is an X-ray analysis apparatus including at least one of polycapillary half lenses that receive light.

  The X-ray irradiation mechanism irradiates the sample with X-rays and the X-ray detection conduit are coaxially integrated, a hole is provided in the secondary target, and fluorescent X-rays from the sample pass through the hole. In the embodiment that is guided to the X-ray detector, only one polycapillary half lens is provided, and the microcapillary half lens that collects the X-ray beam on the minute portion of the sample and the minute portion of the sample. This also serves as a polycapillary half lens that receives the fluorescent X-rays from.

  In a form in which the portion for irradiating the sample with X-rays by the X-ray irradiation mechanism and the X-ray detection conduit are arranged at an angle so as to spread from the combined distal end to both proximal ends, the polycapillary The half lens is a polycapillary half lens that collects an X-ray beam onto a minute portion of the sample at the tip of the X-ray irradiation mechanism, or fluorescence X from the minute portion of the sample at the tip of the X-ray detection conduit. Either a polycapillary half lens that receives a line or both polycapillary half lenses.

  The first aspect of the X-ray analysis method of the present invention uses the X-ray analysis apparatus of the present invention, the step of bringing the tip portion close to the measurement target site of the sample, and the X-ray from the tip of the X-ray irradiation mechanism to the sample. A step of irradiating the beam, and a step of detecting the fluorescent X-rays generated in the sample by the X-ray beam by guiding the X-ray detector to an X-ray detector.

  When applied to an X-ray analysis method for analyzing the surface of a solid sample, the tip of the X-ray beam may be brought close to the surface of the solid sample.

In the conventional fluorescent X-ray analysis, only the solution sample near the X-ray transmission window of the solution cell can be measured with the surface of the solution sample or with the bottom surface irradiation type apparatus. This is due to absorption and attenuation of X-rays in the solution. However, when the present invention is applied, measurement at an arbitrary position in the solution is possible by inserting the X-ray conduit into the solution.
In addition, colloids and sols can be measured as liquid samples.

  In the present invention, the present invention is also applied to an X-ray analysis method for analyzing a solid sample placed in a liquid, and in this case, the tip portion irradiated with the X-ray beam is brought close to the surface of the solid sample placed in the liquid. Just do it.

  The second aspect of the X-ray analysis method of the present invention uses the X-ray analyzer of the present invention to insert the tip of the X-ray analysis device into the measurement target site of the sample, and the X-ray from the tip of the X-ray irradiation mechanism to the sample. A step of irradiating the beam, and a step of guiding the fluorescent X-ray generated in the sample by the X-ray beam to the X-ray detector for detection. When the tip of the conduit is pointed, a soft sample such as a biological sample can be measured.

An X-ray analyzer of the present invention includes a primary X-ray source, an X-ray irradiation mechanism, an X-ray detector, and an X-ray detection conduit, and includes a tip portion of the X-ray irradiation mechanism and an X-ray detection conduit. Since the tips are combined into one, the excitation conduit and the detection conduit are integrated, and the elemental analysis of the sample can be performed without complicated operations such as confocal adjustment.
Further, at least one of a polycapillary half lens that collects an X-ray beam on a minute portion of the sample and a polycapillary half lens that receives fluorescent X-rays from the minute portion of the sample is provided at the combined tip portion. In such a case, elemental analysis of a minute portion such as several tens μm to several hundreds μm on the sample surface can be performed.

An embodiment of the present invention will be described below.
[Example 1]
FIG. 1 is a schematic configuration diagram of an X-ray analyzer.
A primary X-ray source 1 that generates excitation X-rays is connected to an X-ray detection conduit 5 by an X-ray incident conduit 2a that forms part of the X-ray irradiation mechanism.
An X-ray detector 9 is coupled to the proximal end portion of the X-ray detection conduit 5 so that fluorescent X-rays emitted from the sample 7 are guided from the distal end portion through the internal passage 4 to the X-ray detector 9. It has become.

  The X-ray detection conduit 5 receives the primary X-ray beam incident through the X-ray incident conduit 2 a, generates a secondary X-ray beam, and opens the opening 5 a at the tip of the X-ray detection conduit 5. A secondary target 3 for irradiating the sample is provided. A hole for passing X-rays is provided in the center of the secondary target 3. The position of the hole is not limited to the center of the conduit 5 but may be any position that includes the periphery and can pass fluorescent X-rays from the sample.

The secondary target 3 is provided in a ring shape on the inside of the X-ray detection conduit 5 and on the outer periphery of the internal passage 4 in the conduit 5, and the tip is an inclined surface (about 40 degrees from the horizontal plane). Therefore, it is possible to efficiently irradiate the sample with the secondary X-ray beam. Further, a collimator 13 is provided between the internal passage 4 and the X-ray detection conduit 5 for preventing scattered X-rays from the secondary target from directly entering the detector and limiting the observation field of view to the sample 7. It is preferable. This material is preferably a material that does not generate new fluorescent X-rays, such as polytetrafluoroethylene, or the same material as the secondary target.
In this embodiment, the portion of the X-ray detection conduit 5 on the tip side of the secondary target 3 also serves as an X-ray irradiation mechanism.

An X-ray transmissive protective film 6 for closing the opening 5a is provided at the tip of the X-ray detection conduit 5. Thereby, when the conduit 5 is inserted into the sample 7 or the surrounding medium 8, they can be prevented from entering the conduit 5. As the X-ray transparent protective film 6, a polymer film such as a polyimide film can be used, and can be attached to the tip inclined surface of the conduit 5 with an adhesive or the like.
The size of the opening 5a depends on the X-ray beam diameter and the amount of fluorescent X-rays to be detected. For example, about 2 mm is sufficient.

A commercially available X-ray tube is used as the primary X-ray source 1. The X-ray emission window of the X-ray source 1 is provided with an X-ray transmission material such as beryllium.
In order to prevent continuous X-rays derived from the tube and impurity peaks from the tube from affecting the X-ray fluorescence measurement between the X-ray exit window of the X-ray source 1 and the proximal end of the conduit 2a. An appropriate filter 10 may be provided depending on the element to be measured such as zirconium or aluminum.

The secondary target 3 plays a role of changing the optical path of the X-ray beam. As the secondary target 3, for example, a material containing Cu can be used. Thereby, the excitation X-rays irradiated to the sample can be converted from MoKα to CuKα. In general, it is difficult to bend the optical path of the X-ray beam. However, by using such a secondary target, although the X-ray beam has different energy, the optical path can be changed. In the case of FIG. 1, the traveling direction of the X-ray beam is changed by about 90 degrees.
As the X-ray detector 9, an energy dispersive X-ray detector is used. This is to reduce the size of the entire apparatus, but if this restriction is not present, a wavelength dispersion detector may be used. The signal of the detector 9 is subjected to energy analysis through an amplifier, a multi-wave height analyzer or the like, and an X-ray spectrum can be obtained.

As described above, it is desirable to use the same material as the secondary target as the material of the conduits 2a and 5. In this embodiment, the conduit 2a has an inner diameter of 6 mm and an outer diameter of 8 mm. The inside of the conduit becomes an X-ray internal passage, and the X-ray beam passes through almost parallel light.
The conduit 5 also serves to limit the irradiation area when the sample is irradiated with X-rays from the secondary target.
The container containing the sample 7 is placed on the sample position adjusting stage 12 in order to adjust its position. The stage 12 moves in the XYZ directions (X and Y directions are in-plane directions, and the Z direction is a height direction perpendicular to them), and the measurement target region of the sample 7 can be adjusted.

The operation of this embodiment will be described below.
Here, the case where the surface analysis of the solid sample 7 in the medium 8 such as water is performed will be described as an example.
The primary X-ray source 1, the conduit 2 a, the conduit 5 and the X-ray detector 9 are integrated and fixed, and the measurement target region of the sample 7 is adjusted by moving the stage 12.
First, the stage 12 is moved away from the distal end portion of the conduit 5, and the stage 12 is moved in the direction of the conduit 5 (upward in the drawing) so that the conduit 5 is inserted into the medium 8 by raising the stage 12.

The conduit 5 is inserted into the medium 8 and brought close to the surface of the sample 7 so that the primary X-ray beam from the X-ray source 1 is converted into a secondary X-ray beam by the secondary target 3 so that the sample 7 can be irradiated. To do.
As the X-ray source 1, an X-ray tube having molybdenum as a target and having an X-ray emission window of beryllium is used, and a zirconium filter 10 is inserted between the X-ray emission window of the X-ray source 1 and the proximal end portion of the conduit 2 a. Arrange for irradiation with X-rays for excitation.

Excitation X-rays from the X-ray source 1 are received by the secondary target 3, a secondary X-ray beam is generated in the direction of the tip of the conduit 5, and the sample 7 in the medium 8 is irradiated from the opening at the tip. The fluorescent X-rays generated on the surface of the sample 7 are guided to the X-ray detector 9 through the internal passage 4 in the conduit 5 and detected by the detector 9.
At this time, since the opening 5a at the tip of the conduit 5 is sealed with the polymer film, the medium 8 does not enter the internal passage 4 of the conduit 5, and attenuation of X-rays can be suppressed.
As the measurement conditions, for example, the X-ray source 1 is set to a voltage of 40 kV and a current of 30 mA to generate X-rays, and the signal detected by the detector 9 is subjected to energy analysis through an amplifier or a multi-wave height analyzer, for 300 seconds. An X-ray fluorescence spectrum was obtained by integration.

In this embodiment, X-ray irradiation and detection can be performed substantially on the same axis, and the apparatus can be miniaturized.
Moreover, by providing the secondary target 3, the sample can be irradiated with monochromatic X-rays called fluorescent X-rays, and the background of continuous X-rays when measuring the sample can be reduced.
Since the secondary target has a ring shape, X-rays from the secondary target can be irradiated toward the sample 7 in a conical shape. In the conventional X-ray fluorescence analysis, since X-ray irradiation is from one direction, in the embodiment of the present invention, high irradiation efficiency can be realized in principle.
Furthermore, since the secondary target 3 is provided in a ring shape inside the X-ray detection conduit and on the outer periphery of the internal passage in the X-ray detection conduit, the fluorescent X-rays generated from the sample are the ring-shaped target. 3 is led to the detector 9 through the internal passage 4 from the hole 3 and is detected with excellent detection efficiency.

Next, another embodiment of the present invention will be described.
[Example 2]
FIG. 2 is a schematic configuration diagram of the X-ray analyzer.
The primary X-ray source 1 is connected to an X-ray detection conduit 5 by an X-ray incident conduit 2a. An X-ray detector 9 is coupled to the proximal end portion of the X-ray detection conduit 5, and fluorescent X-rays emitted from the minute portion 11 are guided to the X-ray detector 9 through the internal passage 4 from the opening of the distal end portion. It has come to be.

  An X-ray irradiation conduit 2b is provided in the X-ray detection conduit 5. The primary X-ray beam incident from the X-ray incidence conduit 2a is received in the X-ray irradiation conduit 2b, and a secondary X-ray is received. A secondary target 3 for irradiating the line beam toward the tip is provided. An X-ray irradiation mechanism is constituted by the X-ray incident conduit 2a and the X-ray irradiation conduit 2b.

In this embodiment, the X-ray detection conduit 5 and the X-ray irradiation conduit 2b are double tubes and are arranged substantially in parallel. The fluorescent X-rays in the backscattering direction from the minute part 11 can be incident on the X-ray detection conduit 5.
Further, a double tube provided with the X-ray detection conduit 5 in the X-ray irradiation conduit 2b may be used.

  Since the X-ray detection conduit 5 is provided with an X-ray permeable protective film 6 for closing the opening at the tip of the X-ray detection conduit 5, when the conduit 5 is inserted into the minute portion 11 or the surrounding medium, they are connected to the conduit. Intrusion can be prevented. As the X-ray transparent protective film 6, the same film as that in Example 1 can be attached.

  The primary X-ray source 1 can be the same as that of the first embodiment. Between the X-ray emission window of the X-ray source 1 and the proximal end portion of the conduit 2a, X-rays derived from a tube are present. A filter 10 is provided to prevent the fluorescent X-ray measurement from being affected.

The same secondary target 3 and X-ray detector 9 as those in the first embodiment can be used.
As the conduits 2a, 2b and 5, conduits of the same material as the secondary target can be used as in the first embodiment.

Next, the operation of this embodiment will be described. Here, the case where the site | part inside the sample 7a which can insert a needle | hook like a biological sample is measured is demonstrated.
The tip of the conduit 5 is inserted into the sample 7a to approach the micro site 11.
As the X-ray source 1, an X-ray tube having molybdenum as a target and an X-ray emission window of beryllium is used, and a zirconium filter 10 is placed between the X-ray emission window of the X-ray source 1 and the proximal end portion of the conduit 2 a. It arrange | positions and irradiates the secondary target 3 with the X-ray for excitation through the conduit | pipe 2a.

Excitation X-rays from the X-ray source 1 are received by the secondary target 3, a secondary X-ray beam is generated in the direction of the distal end of the conduit 2b, and the minute portion 11 is irradiated from the opening at the distal end. The fluorescent X-rays generated by the minute portion 11 are guided to the X-ray detector 9 through the internal passage 4 in the conduit 5 and detected by the detector 9.
At this time, since the opening at the tip of the conduit 5 is covered with the polymer film, the medium 8 does not enter the internal passage 4 of the conduit 5 and attenuation of X-rays can be suppressed.

  In the present embodiment, the X-ray detection conduit 5 and the X-ray irradiation conduit 2b are made substantially parallel and one is arranged inside the other, so that the conduit 5 is brought close to the minute portion 11, for example. Thus, the elemental concentration of the minute part 11 in the sample can be measured.

Next, still another embodiment of the present invention will be described.
[Example 3]
FIG. 3 is a schematic configuration diagram of the X-ray analyzer.
The primary X-ray source 1 is connected to an X-ray irradiation conduit 2b by an X-ray incident conduit 2a. The X-ray irradiation mechanism includes an X-ray incident conduit 2a and an X-ray irradiation conduit 2b.
The distal end portion of the X-ray irradiation conduit 2b is united with the distal end portion of the X-ray detection conduit 5, and both base end portions are arranged with an angle extending from the distal end portion toward both base end portions.
An X-ray detector 9 is coupled to the proximal end portion of the X-ray detection conduit 5, and fluorescent X-rays emitted from the sample 7 are guided to the X-ray detector 9 through the internal passage 4 from the opening of the distal end portion. It is like that.

The X-ray irradiation conduit 2b receives the primary X-ray beam incident from the X-ray incident conduit 2a and irradiates the secondary X-ray beam toward the opening at the tip of the X-ray irradiation conduit 2b. Secondary target 3 is provided. However, the secondary target 3 may be removed and the X-ray source 1 may be disposed directly on the end face of the X-ray irradiation conduit 2b.
In this embodiment, the proximal end portion of the X-ray detection conduit 5 and the proximal end portion of the X-ray irradiation conduit 2b are disposed so as to extend about 45 degrees, but are not particularly limited. In Example 2, an attempt was made to realize an arrangement in which this angle is close to 0 degrees.

  Since the X-ray transparent protective film 6 for closing the opening is provided at the tip, when the conduits 2b and 5 are inserted into the sample 7 or the surrounding medium 8, they are prevented from entering the conduit. Can be prevented. As the X-ray transparent protective film 6, the same film as that in Example 1 can be attached.

  As the primary X-ray source 1, the same one as in Example 1 can be used. Between the X-ray emission window of the X-ray source 1 and the proximal end portion of the conduit 2 a, X-rays derived from the tube are fluorescent X A filter 10 is provided to prevent the line measurement from being affected.

The same secondary target 3 and X-ray detector 9 as those in the first embodiment can be used.
The conduits 2a, 2b, and 5 are made of glass, but may be made of other materials.

  The container containing the sample 7 is placed on the sample position adjusting stage 12 in order to adjust its position. The stage 12 moves in the XYZ directions (X and Y directions are in-plane directions, and the Z direction is a height direction perpendicular to them), and the measurement target region of the sample 7 in the medium 8 can be adjusted. .

Next, the operation of this embodiment will be described.
The container containing the sample 7 is kept away from the tip of the X-ray detection conduit 5, the stage 12 is moved upward in the drawing, and the conduit 5 is inserted into the solvent 8.
As the X-ray source 1, an X-ray tube having molybdenum as a target and an X-ray emission window of beryllium is used, and a zirconium filter 10 is placed between the X-ray emission window of the X-ray source 1 and the proximal end portion of the conduit 2 a. Arrange for irradiation with X-rays for excitation.

Excitation X-rays from the X-ray source 1 are received by the secondary target 3, a secondary X-ray beam is generated in the direction of the distal end of the conduit 2b, and the surface of the sample 7 is irradiated from the opening at the distal end. The fluorescent X-rays generated by the sample 7 are guided to the X-ray detector 9 through the internal passage 4 in the conduit 5 and detected by the detector 9.
At this time, since the opening at the tip of the conduit 5 is covered with the polymer film, the medium 8 does not enter the internal passage 4 of the conduit 5.

  In this embodiment, the conduit 2b and the conduit 5 are arranged so that the axes of their internal passages cross each other on their extension lines, and each tip side is moved into the solvent 8 by moving the solvent 8. Insert into. Since the distal ends of both the conduits 2b and 5 are arranged close to the distance at which the fluorescent X-rays generated on the surface of the sample 7 reach the distal end of the conduit 5 by the X-rays irradiated from the distal end of the conduit 2b, complicated adjustments are made. Elemental analysis can be performed without having to Further, since the X-ray detection conduit 5 and the X-ray irradiation conduit 2b are spatially separated from each other, it is possible to secure an arrangement space for the X-ray source 1, the detector 9, and the like.

[Measurement of solution sample]
Analyzing metal elements (for example, electrode surfaces) in liquids and aqueous solutions is essential for improving battery materials and plating materials, but until now there has been no direct method for directly observing the surface of materials such as metals in liquids. Various surface analysis methods were applied after operations such as taking out these materials.
However, in the present invention, the surface of the metal in the aqueous solution or the surface of the electrode material in the electrolytic solution can be observed in the aqueous solution simply by immersing the glass collimator as in Examples 1 to 3 in the aqueous solution to be measured. It becomes possible to monitor the progress of the corrosion of the metal surface in seawater and to directly measure the metal ion concentration in the aqueous solution.

[Measured nondestructively]
In the fluorescent X-ray analysis method, there is a request for nondestructive measurement of the inside of the sample, but no method other than the method using the X-ray condenser lens shown in Non-Patent Document 1 has been proposed so far. In the microscopic fluorescent X-ray analysis, X-rays are irradiated from the outside of the sample, and only the fluorescent X-rays emitted from the sample to the atmosphere side (or vacuum side) have been detected. Therefore, the depth of the sample that can be measured from the surface has been limited to several microns to several millimeters.

  However, in the present invention, when a collimator having a pointed tip is used as a conduit, or an injection needle used for medical solution injection or blood collection in the medical field, the conduit is limited to a soft sample. Directional restrictions are relaxed and non-destructive measurements can be made inside a solid sample several centimeters from the sample surface.

Here, “non-destructive” in the present invention means that the conduit is inserted, but the state is restored to the current state by removing the conduit after the measurement. In particular, in the case where the sample is a living biological sample, it can be said that the living body recovers and becomes closer to nondestructive measurement.
Since the conduit is inserted into the sample, it is not a non-destructive measurement in a strict sense, but it becomes a non-destructive state as compared with the method of cutting the cross section of the sample, and the state becomes more non-destructive as the conduit is made thinner.

  In the present invention, the tip of the conduit 2b that guides X-rays irradiated to the sample by the X-ray irradiation mechanism and the tip of the X-ray detection conduit 5 are three-dimensionally such that the axis of the internal passage intersects with each other on the extension line. Since it is arranged inside the sample so as to connect the intersections to each other, elemental analysis of the measurement site inside the sample can be performed non-destructively and, if there is a length of the conduit, several centimeters or more It is possible to measure deep portions, and the restriction in the depth direction is relaxed.

  When an injection needle is used as the conduit, a commercially available injection needle having an inner diameter of about 0.2 mm to 1.0 mm can be easily obtained. An injection needle having a tip diameter of 0.2 mm or less can be prepared. When such a fine injection needle is used as a conduit, a micro space on the order of μm can be measured.

  In addition, the size of the region to be analyzed inside the sample depends on the thickness of the tip of the conduit, but by using an appropriate needle-like one, a minute space having a size of several hundred μm to several mm, Alternatively, a space smaller than that can be measured.

FIG. 4 is an X-ray spectrum obtained when the solid sample was subjected to elemental analysis using the apparatus of Example 1. The horizontal axis represents energy and the vertical axis represents intensity. In the description of the apparatus of the first embodiment, the sample 7 is disposed in the medium 8. However, in this measurement, the sample 7 is not immersed in a medium such as an aqueous solution.
As the sample 7, an Fe plate having a thickness of 0.5 mm was used.
As measurement conditions, the X-ray source (target is Mo) 1 is set to a voltage of 20 kV and a current of 40 mA to generate X-rays, a ring-shaped Cu is used as a secondary target, and the signal detected by the detector 9 is Energy analysis was performed through an amplifier or a multi-wave height analyzer, and integration was performed for 100 seconds to obtain a fluorescent X-ray spectrum. The distance between the sample 7 and the tip of the conduit 5 was set to about 2 mm.

  In addition to Cu fluorescent X-rays from the secondary target, Fe fluorescent X-rays from the sample were observed, so it was confirmed that the sample could be used as a fluorescent X-ray analyzer.

FIG. 5 is an X-ray spectrum when elemental analysis in a liquid sample is performed using the apparatus of Example 3. The horizontal axis represents energy and the vertical axis represents intensity.
As the liquid sample, 10 mL (2800 ppm) of NiSO ₄ was used. The concentration of NiSO ₄ is set to a standard plating solution concentration.
As a measurement condition, an X-ray source (target is Mo) 1 is set to a voltage of 20 kV and a current of 40 mA to generate X-rays, and a secondary target having a Cu surface coated with Zn is used. The detected signal was subjected to energy analysis through an amplifier or a multi-wave height analyzer and integrated over 300 seconds to obtain a fluorescent X-ray spectrum. “Preset Time” is the measurement time. The reason why the Zn plate is used as the secondary target is to efficiently excite Ni fluorescent X-rays.

ROI Intensity (peak area intensity) is
ZnKα: 19802 (NET) 40059 (GROSS),
CuKα: 778 (NET) 11438 (GROSS),
NiKα: 21798 (NET) 25075 (GROSS),
FeKα: 1255 (NET) 2795 (GROSS),
It became.
Where NET means net peak intensity minus background intensity,
GLOSS means total peak intensity including background intensity.

The concentration of Ni was 2800 ppm, and fluorescent X-rays in the liquid sample could be obtained by inserting the conduit 5 of FIG. 3 into the liquid sample. From this result, it was confirmed that the present invention is effective as a simple method for monitoring the concentration of metal elements in a liquid (for example, waste solution, plating bath, etc.).
Since the secondary target is a Cu surface coated with Zn, Cu was also detected in the spectrum of FIG.

FIG. 6 shows the relationship between the sample concentration of the liquid sample and the detected intensity when the apparatus of Example 3 is used.
As the liquid sample, one having a different concentration of CoSO ₄ aqueous solution was used.
As measurement conditions, the same apparatus as in Example 3 was used, the X-ray source 1 was set to a voltage of 20 kV and a current of 40 mA to generate X-rays, and the signal detected by the detector 9 was passed through an amplifier or a multi-wave height analyzer. X-ray fluorescence spectrum was obtained by energy analysis and integration over 300 seconds.

In addition to plotting an average value when five measurements are performed on each liquid sample, an error bar corresponding to the standard deviation is also shown. The correlation coefficient R was 0.9994, confirming a good linear relationship. Furthermore, when the lower limit of detection was evaluated from the relationship between the slope of this straight line and the concentration zero, that is, the background intensity at the CoKα peak in the blank solution sample, it was 27.9 ppm. This measurement result can be used as a calibration curve when measuring a CoSO ₄ aqueous solution sample.

FIG. 7 is an X-ray spectrum when elemental analysis of a solid sample in a liquid is performed using the apparatus of Example 3. The horizontal axis represents energy and the vertical axis represents intensity.
As the liquid, 10 mL (2800 ppm) of NiSO ₄ was used, and as the sample 7, an iron plate having a thickness of 0.5 mm was used.
As measurement conditions, the X-ray source 1 is set to a voltage of 20 kV and a current of 40 mA to generate X-rays, and the signal detected by the detector 9 is analyzed for energy through an amplifier or a multi-wave height analyzer and integrated for 300 seconds. Thus, a fluorescent X-ray spectrum was obtained. The distance between the sample 7 and the tip of the conduit 5 was set to about 200 μm.

ROI Intensity (peak area intensity) is
ZnKα: 18714 (NET) 36927 (GROSS),
CuKα: 1475 (NET) 11199 (GROSS),
NiKα: 17672 (NET) 24434 (GROSS),
FeKα: 22747 (NET) 25652 (GROSS),
It became.

The characteristic X-ray of Fe can be clearly measured from the X-ray spectrum measured in an aqueous solution with respect to the Fe metal material in the NiSO ₄ aqueous solution. For example, direct in situ analysis of the electrode surface in the electrolytic solution, metal in seawater It can be seen that it can be applied to monitoring corrosion processes.

FIG. 8 is an X-ray spectrum when elemental analysis of a solid sample in a liquid is performed using the apparatus of Example 3. The horizontal axis represents energy and the vertical axis represents intensity.
NiSO ₄ 10 mL (2800 ppm) was used as the liquid, and 0.05 mm thick Ni plate was used as the sample 7.
As measurement conditions, the X-ray source 1 is set to a voltage of 20 kV and a current of 40 mA to generate X-rays, and the signal detected by the detector 9 is analyzed for energy through an amplifier or a multi-wave height analyzer and integrated for 300 seconds. Thus, an X-ray fluorescence spectrum was obtained. The distance between the sample 7 and the tip of the conduit 5 was set to about 200 μm.

ROI Intensity (peak area intensity) is
ZnKα: 8775 (NET) 45968 (GROSS),
CuKα: −4667 (NET) 15517 (GROSS),
NiKα: 100977 (NET) 100996 (GROSS),
FeKα: 1013 (NET) 3953 (GROSS),
It became.

A characteristic X-ray of Ni can be clearly measured from an X-ray spectrum measured in an aqueous solution with respect to a Ni metal material in an NiSO ₄ aqueous solution. For example, direct in-situ analysis of an electrode surface in an electrolytic solution, or in seawater It can be seen that it can be applied to monitoring metal corrosion processes.

  4 to 8 show the results of measurement using the apparatus shown in Examples 1 and 3. In Example 2, it is expected that similar or higher results will be obtained.

[Example 4]
FIG. 9 shows the embodiment shown in FIG. 1 in which a polycapillary half lens 20 is attached as an X-ray condensing element between the secondary target 3 and the tip opening at the tip of the X-ray detection conduit 5. Except for the point that the polycapillary half lens 20 is provided, the other configuration is the same as that of the embodiment shown in FIG.

  The polycapillary half lens 20 is a bundle of many capillary lenses. As shown in the perspective view of FIG. 10, the polycapillary half lens 20 has a wide end surface 21a and a narrow end surface 21b formed in parallel to each other so that the diameter decreases from the end surface 21a toward the end surface 21b. It is bundled while changing. The outer shape has a shape in which the side surface of the truncated cone is curved so as to swell slightly outward. In this example, the cross-sectional shape perpendicular to the axial direction is a circle, but it may be a regular polygon. In the polycapillary half lens 20, parallel X-rays incident on the end surface 21a having a large area propagate while being totally reflected in the capillary, and exit from the end surface 21b having a small area and are focused on the focal point.

  The polycapillary half lens 20 has a function of condensing secondary X-rays generated from the secondary target 3 and condensing it on a minute portion on the sample 7 when irradiating the sample 7 from the tip portion. Further, the fluorescent X-rays generated from the minute portion of the sample 7 are collected by the polycapillary half lens 20 and guided to the X-ray detector 9 as substantially parallel X-rays. More specifically, secondary X-rays from the target 3 can be focused and irradiated on a minute portion of about several tens of μm on the sample through the peripheral portion of the polycapillary half lens 20, The fluorescent X-rays generated from an area of several tens of μm are then condensed through the center of the polycapillary half lens 20 and guided to the detector 9 from the opening of the ring-shaped target 3 through the internal passage 4. As described above, in this embodiment, the polycapillary half lens 20 realizes both the function of irradiating X-rays to the minute part and the function of receiving the fluorescent X-rays generated from the minute part by one polycapillary lens. Yes.

[Example 5]
FIG. 11 shows the embodiment shown in FIG. 3 in which a polycapillary half lens 20a is provided at the tip of the X-ray irradiation conduit 2b. Except for the point that the polycapillary half lens 20a is provided, the other configuration is the same as that shown in FIG. The fluorescent X-rays generated from the sample 7 are guided to the detector 9 as in the embodiment of FIG.

In the case of this embodiment, secondary X-rays generated from the target 3 are condensed by the polycapillary half lens 20a and irradiated onto a minute region on the sample 7. The configuration and function of the polycapillary half lens 20a are the same as those described in the embodiments of FIGS.
Also in this embodiment, only a minute portion of the sample 7 can be irradiated with secondary X-rays.

[Example 6]
FIG. 12 shows the embodiment shown in FIG. 3 in which a polycapillary half lens 20b for receiving fluorescent X-rays is provided at the tip of the X-ray detection conduit 5. In FIG. Except for the point that the polycapillary half lens 20b is provided, the other configuration is the same as that shown in FIG.

  In this embodiment, the sample 7 is excited by secondary X-rays from the target 3, and the generated fluorescent X-rays are received by the polycapillary half lens 20 b and guided to the detector 9. The polycapillary half lens 20b can receive only fluorescent X-rays from a minute part on the sample 7, and even if the surface of the sample 7 is excited to a certain extent by secondary X-rays, the polycapillary half lens 20b Only the fluorescent X-rays from a specific minute portion among them are received by the polycapillary half lens 20b and guided to the detector 9.

[Example 7]
FIG. 13 shows an embodiment shown in FIG. 3, in which a polycapillary half lens 20a for irradiating a minute portion of the sample 7 with secondary X-rays is provided at the tip of the X-ray irradiation conduit 2b, and two on the sample. A polycapillary half lens 20b for receiving fluorescent X-rays generated from a minute portion irradiated with the next X-ray is provided at the distal end portion of the X-ray detection conduit 5. The polycapillary half lens 20a and the polycapillary half lens 20b are arranged so as to focus on the same minute portion on the surface of the sample 7.

  In this embodiment, secondary X-rays from the target 3 are condensed and irradiated on a minute portion on the sample 7 by the polycapillary half lens 20a, and fluorescent X-rays generated from the minute portion are received by the polycapillary half lens 20b. Then, it is guided to the detector 9.

  Preliminary experiments for examining the light condensing performance of the polycapillary half lenses 20, 20a, 20b used in Examples 4 to 7 were conducted.

  FIG. 14 shows the specifications of the polycapillary half lens 30 used. The polycapillary half lens 30 is used as the polycapillary half lens 20, 20a, 20b in the embodiment. The outer shape of the polycapillary half lens 30 has a substantially regular hexagonal frustum shape. The area of both end faces 31a and 31b is such that one end face 31a is wider than the other end face 31b, the maximum dimension of the end face 31a is 10 mm, the maximum dimension of the end face 31b is 8 mm, and the length between the end faces 31a and 31b. The height is 50 mm. The side surface is not a flat surface in a strict sense, but is curved so as to swell slightly outward.

  When parallel X-rays are incident from the larger end surface 31a of the polycapillary half lens 30, the X-rays emitted from the smaller end surface 31b form a minute image at the position of the focal length. Its focal length is 29.8 mm, and the image size is designed to be 110 μm in the direct system.

Next, the actual light collecting performance of the polycapillary half lens 30 was examined.
FIG. 15 is a preliminary experimental apparatus for confirming that the polycapillary half lens 30 actually guides X-rays. Secondary X-rays from the target 3 were guided by the polycapillary half lens 30 and irradiated onto the iron plate as the sample 7. The thickness of the iron plate is 0.5 mm. X-ray fluorescence generated from the iron plate 7 was directly received and detected by a Si-PIN detector as the detector 9.

  A spectrum in which fluorescent X-rays from the sample 7 are detected is shown in FIG. The irradiation conditions of the primary X-ray source at this time used a Mo target, set the voltage to 40 KV and the current to 40 mA, and generated X-rays. The measurement is an integration result over 300 seconds. Iron Kα rays and Kβ rays are detected, and it can be confirmed that the polycapillary half lens 30 is surely guiding X-rays.

  FIG. 17 also confirms that the polycapillary half lens 30 guides X-rays. Secondary X-rays from the target 3 are directly guided to the Si-PIN detector as the detector 9 by the polycapillary half lens 30. Secondary X-rays from the target 3 were detected. The irradiation conditions of the primary X-ray source at this time used a Mo target, set the voltage to 40 KV and the current to 40 mA, and generated X-rays. FIG. 18 shows a detection spectrum at that time, and secondary X-ray copper Kα and Kβ rays are detected. The measurement is an integration result over 1000 seconds.

  Next, an experiment for measuring the field of view of the polycapillary half lens 30 was performed. As shown in FIG. 19, a polycapillary half lens 30 is attached to the X-ray detection conduit 5, and fluorescent X-rays incident on the polycapillary half lens 30 are guided to a Si-PIN detector as a detector 9 for detection. It is what I did. A tungsten wire 40 having a diameter of 30 μm was used as a sample, and the primary X-ray from the X-ray source 1 was irradiated to the tungsten wire 40 as parallel X-rays by a collimator 42. The diameter of the X-ray beam emitted from the collimator 42 is 3 mm.

  The tungsten wire 40 is fixed on a flat table, and the primary X-rays are irradiated so that the fluorescent X-rays of tungsten are generated from the fixed position. The polycapillary half lens 30 attached to the detector 9 is supported so as to be movable in a horizontal plane together with the detector 9, and is scanned at a pitch of 10 μm across the wire 40 as indicated by the X direction in the figure. The intensity of tungsten Lα rays generated from the tungsten wire 40 was plotted. The result is shown in FIG. The irradiation conditions of the primary X-ray source at this time used a Mo target, set the voltage to 40 KV and the current to 30 mA, and generated X-rays. The measured value of each plot in FIG. 20 is an integration result over 60 seconds at each position. When the measurement result of FIG. 20 is regarded as a Gaussian distribution and the half-value width is obtained, it is 152 μm. From this, the field of view of the polycapillary half lens 30 can be evaluated as 152 μm.

  By providing this polycapillary half lens 30 in at least one of the portion that irradiates the sample with X-rays and the portion that condenses the fluorescent X-rays as shown in Examples 4 to 7, fluorescent X-ray analysis of only a minute portion Can be performed.

The present invention requires a space for providing a polycapillary half lens in the case where the polycapillary half lens is provided inside, so that there are some restrictions on the shape and size of the conduit. As long as the half lens is not provided, the shape of the end of the conduit and the direction of insertion into the sample are not limited to the above embodiment, and other shapes and arrangements are possible. For example, other shapes such as a needle can be used as the conduit. The material is not particularly limited as long as it can conduct X-rays, and may be a quartz glass capillary.
Further, if the polycapillary half lens is not provided inside, the conduit does not have to be hollow inside, and may be solid as long as it is a material that transmits X-rays. Therefore, it is not necessary to provide a cover for preventing the sample from entering the tip of the conduit.
Furthermore, regardless of whether or not a polycapillary half lens is provided therein, the distal end portion of the conduit does not need to be an opening, as long as it can transmit X-rays.

In the case where the polycapillary half lens is not provided inside, if the measurement sample is a living organism, it is possible to open it after measurement and measure it again after a predetermined time and measure the change over time of a specific element. become.
In the case where a polycapillary half lens is not provided in the interior, a deep portion can be measured by simply increasing the length of the conduit. Therefore, measurement can be performed at a plurality of locations on a single solid biological sample.
In the case where the polycapillary half lens is not provided inside, it is also possible to measure a specific part of the human body such as cancer cells generated in the body.

  INDUSTRIAL APPLICABILITY The present invention can be used for an X-ray analyzer that performs elemental analysis on biological samples, solid samples, liquid samples, and solid samples in liquids.

It is a schematic block diagram which shows the 1st Example of this invention. It is a schematic block diagram which shows the 2nd Example of this invention. It is a schematic block diagram which shows the 3rd Example of this invention. It is the result at the time of performing the elemental analysis of the solid sample in a liquid using the apparatus of Example 1. FIG. It is a result at the time of performing the elemental analysis in a liquid sample using the apparatus of Example 3. FIG. 3 shows a calibration curve of a liquid sample when the apparatus of Example 3 is used. It is the result at the time of performing the elemental analysis of the solid sample in a liquid using the apparatus of Example 3. FIG. It is the result at the time of performing the elemental analysis of the solid sample in a liquid using the apparatus of Example 3. FIG. It is a schematic block diagram which shows Example 4 provided with the polycapillary half lens. It is a schematic perspective view which shows the polycapillary half lens used in the Example. It is a schematic block diagram which shows Example 5 provided with the polycapillary half lens. It is a schematic block diagram which shows Example 6 provided with the polycapillary half lens. It is a schematic block diagram which shows Example 7 provided with the polycapillary half lens. It is the front view and both ends which show the specification of the used polycapillary half lens. It is a schematic front sectional view showing a preliminary experimental apparatus for confirming the function of the polycapillary half lens. It is a figure which shows the obtained fluorescence X-ray spectrum. It is a schematic front sectional view showing a preliminary experimental apparatus for confirming other functions of the polycapillary half lens. It is a figure which shows the obtained secondary X-ray spectrum. It is a schematic front sectional view showing a preliminary experimental apparatus for measuring the field of view of a polycapillary half lens. It is a graph which shows intensity distribution of the obtained tungsten L alpha ray.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 X-ray source 2a X-ray incident conduit 2b X-ray irradiation conduit 4 Internal passage 5 X-ray detection conduit 5a Opening 6 X-ray permeable protective film 7 Sample 8 Solvent 9 Detector 10 Filter 12 Sample position adjusting stage 20 , 20a, 20b, 30 Polycapillary half lens

Claims (18)

An X-ray irradiation mechanism for irradiating the sample with an X-ray beam from the tip;
An X-ray detector for detecting fluorescent X-rays emitted from the sample;
An X-ray having the X-ray detector at the proximal end, arranged on the same side as the X-ray irradiation mechanism with respect to the sample, and guiding fluorescent X-rays incident from the tip to the X-ray detector through an internal passage A detection conduit;
X-ray analysis in which the tip of the X-ray irradiation mechanism and the tip of the X-ray detection conduit are united so that the sample is irradiated with the X-ray beam and fluorescent X-rays from the sample are incident apparatus.   A base end portion of the X-ray irradiation mechanism is coupled to a primary X-ray source, and a secondary X-ray beam is generated in the X-ray irradiation mechanism by receiving a primary X-ray beam from the primary X-ray source, The X-ray analyzer according to claim 1, further comprising a secondary target that irradiates the sample through the tip.   The portion for irradiating the sample with X-rays by the X-ray irradiation mechanism and the X-ray detection conduit are integrated on the same axis, and a hole is provided in the secondary target, and fluorescent X-rays from the sample pass through the hole. The X-ray analyzer according to claim 2, wherein the X-ray analyzer is guided to an X-ray detector.   The X-ray analyzer according to claim 2, wherein a portion of the X-ray irradiation mechanism that irradiates the sample with X-rays is disposed in an X-ray detection conduit.   The portion for irradiating the sample with X-rays by the X-ray irradiation mechanism forms an X-ray irradiation conduit disposed substantially parallel to the X-ray detection conduit in the X-ray detection conduit, and the secondary target is an X-ray irradiation conduit. The X-ray analysis apparatus according to claim 4, wherein the X-ray analysis apparatus is disposed inside.   The X-ray analyzer according to claim 5, wherein the conduit is a collimator or an injection needle having a pointed tip.   The portion for irradiating the sample with X-rays by the X-ray irradiation mechanism and the X-ray detection conduit are arranged at an angle so as to spread from the combined distal end to both proximal ends. 2. The X-ray analyzer according to 2.   The combined distal end portion includes at least one of a polycapillary half lens that collects an X-ray beam on a minute portion of the sample and a polycapillary half lens that receives fluorescent X-rays from the minute portion of the sample. The X-ray analyzer according to claim 1 or 2. The portion for irradiating the sample with X-rays by the X-ray irradiation mechanism and the X-ray detection conduit are integrated on the same axis, and a hole is provided in the secondary target, and fluorescent X-rays from the sample pass through the hole. Through to the X-ray detector,
The polycapillary half lens is provided with only one, and serves as both a polycapillary half lens that collects an X-ray beam onto a minute portion of the sample and a polycapillary half lens that receives fluorescent X-rays from the minute portion of the sample. The X-ray analyzer according to claim 8. The portion for irradiating the sample with X-rays by the X-ray irradiation mechanism and the X-ray detection conduit are disposed at an angle so as to spread from the combined distal end toward both proximal ends,
9. The X-ray analysis apparatus according to claim 8, wherein the polycapillary half lens is a polycapillary half lens that focuses an X-ray beam onto a minute portion of a sample at a tip portion of the X-ray irradiation mechanism. The portion for irradiating the sample with X-rays by the X-ray irradiation mechanism and the X-ray detection conduit are disposed at an angle so as to spread from the combined distal end toward both proximal ends,
9. The X-ray analysis apparatus according to claim 8, wherein the polycapillary half lens is a polycapillary half lens that receives fluorescent X-rays from the minute portion of the sample at the tip of the X-ray detection conduit. The portion for irradiating the sample with X-rays by the X-ray irradiation mechanism and the X-ray detection conduit are disposed at an angle so as to spread from the combined distal end toward both proximal ends,
As the polycapillary half lens, a polycapillary half lens for condensing an X-ray beam onto a minute portion of the sample at the tip of the X-ray irradiation mechanism, and from the minute portion of the sample at the tip of the X-ray detection conduit The X-ray analyzer according to claim 8, further comprising a polycapillary half lens that receives fluorescent X-rays.   The X-ray analyzer according to any one of claims 1 to 12, wherein an X-ray transparent protective film that closes an opening is provided at the combined distal end portion.   The X-ray analyzer according to claim 13, wherein the X-ray transparent protective film is a polymer film. A step of bringing the tip of the X-ray analyzer according to any one of claims 1 to 14 close to a measurement target site of a sample;
Irradiating the sample with an X-ray beam from the tip of the X-ray irradiation mechanism;
Introducing fluorescent X-rays generated in the sample by the X-ray beam to the X-ray detector and detecting;
An X-ray analysis method comprising:   The X-ray analysis method according to claim 15, wherein the X-ray analysis method is applied to an X-ray analysis method for analyzing a surface of a solid sample, and the tip portion irradiated with the X-ray beam is brought close to the surface of the solid sample.   16. The method according to claim 15, which is applied to an X-ray analysis method for analyzing a solid sample placed in a liquid, and causes the tip portion that irradiates the X-ray beam to approach the surface of the solid sample placed in the liquid. X-ray analysis method. Inserting the tip of the X-ray analyzer according to claim 6 into a measurement target site of a sample;
Irradiating the sample with an X-ray beam from the tip of the X-ray irradiation mechanism;
Introducing fluorescent X-rays generated in the sample by the X-ray beam to the X-ray detector and detecting;
An X-ray analysis method comprising:

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