TWI444614B - Micro X-ray measuring device - Google Patents

Description

Micro-section X-ray measuring device

According to the present invention, the position is determined by the coordinate measurement by the optical microscope, and even if the element contained in the substrate (substrate) is the same as the element contained in the sample, the measurement of the minute portion can be performed. Micro-section X-ray measuring device.

Various methods such as microscopic infrared spectroscopy, micro-Raman spectroscopy, and electron beam-excited fluorescent X-ray analysis are used for measuring a small portion of a large sample or a small sample mounted on various substrates. Was developed. Among them, infrared spectroscopy and Raman spectroscopy are particularly suitable for the measurement of organic materials. Further, the electron beam analysis method is generally applied to the measurement of inorganic materials or metals, and in particular, it can be widely used even if it is measured in a vacuum, even if a light element such as aluminum (Al) can be measured. However, in the electron beam analysis method, it is necessary to insert the sample into a vacuum, so that it is not easy to improve the processing capability of the measurement, and it is particularly difficult to measure the sample on a large sample or a large substrate.

In the past, for example, Patent Document 1 below discloses that an X-ray measuring device that attempts to achieve high sensitivity/high measurement processing speed for the purpose of measurement of a minute portion has been developed for the film formation control of the semiconductor manufacturing step. In the apparatus of Patent Document 1, in order to control the film thickness with high precision, it takes about 5 seconds to 20 seconds to measure the point (micro portion) of the measurement, and it takes a relatively long time. On the other hand, as disclosed in the following Patent Document 2, Patent Document 3, or Patent Document 4, an apparatus for measuring optical measurement and X-ray measurement has been developed, but an apparatus for measuring by an optical microscope is emphasized, and X-ray measurement is performed. Some do not use optical components, regardless of the efficiency of the fluorescent X-rays or the background noise from the substrate, so especially for the measurement of tiny metals, only micrograms to milligrams, a small amount of nanograms Metal measurement is impossible.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-153767

[Patent Document 2] International Publication WO2009/093341

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-198485

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-258114

However, a large sample or a fluorescent X-ray measurement of a sample mounted on a large substrate needs to be performed in the atmosphere. However, in such a case, there is a problem that the X-ray is attenuated in the atmosphere.

In addition, in order to perform the X-ray measurement of a small portion, it is necessary to focus the X-ray beam on the X-ray optical element of a small cross-sectional area, and it is necessary to have an optical microscope, and further, it must be directed to the inclusion of the fluorescent X-ray. The configuration of the X-ray detector for measurement is taken down.

Therefore, the present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide an element contained in a substrate (substrate) on which a sample is mounted, and an element contained in the sample. In the same manner, it is also possible to perform a minute-part X-ray measuring device for measuring the composition of a small portion of stability.

In the present invention, as described above, in view of the measurement of a large sample or a fluorescent X-ray of a sample mounted on a large substrate (substrate), it is necessary to carry out the reaction in the atmosphere. In particular, it is achieved by the knowledge and insights of the inventors described below. In other words, in the case of performing fluorescent X-ray measurement in the atmosphere, for example, a fluorescent X-ray (characteristic X-ray energy of 1.5 keV) emitted from aluminum (Al) of a light element is attenuated every 1 mm in the atmosphere. About 20%. On the other hand, the fluorescent X-rays emitted from transition metal elements such as iron (Fe) or copper (Cu) (characteristic X-ray energies are 6.8 keV and 8.0 keV, respectively), and the distance in the atmosphere is several mm. Almost no attenuation. In other words, if the distance from the sample to the detecting element of the detector (the path (light path) of the fluorescent X-ray in the atmosphere) is shortened as much as possible, for example, if it is set to 5 mm or less, the degree of 1.5 keV can be made. The transmittance of the fluorescent X-ray in the atmosphere is as high as 30%, whereby the fluorescent X-ray of an element larger than the atomic order of aluminum (Al) can be detected.

Therefore, according to the knowledge of the inventors mentioned above, in order to achieve the above object, first, a micro X-ray measuring device including an X-ray generating device and an X-ray emitted from the X-ray generating device is provided. An X-ray optical element that is focused on a cross-sectional area having a diameter of 50 μm or less on a measurement sample, an X-ray detector that detects a fluorescent X-ray emitted from the measurement sample, and an optical image of an optical image at a position where the X-ray irradiation is possible a microscope, and a sample relative movement mechanism capable of scanning and positioning the sample in a secondary direction and adjusting the position of the air path in a height direction of 5 mm or less; by image recognition according to the optical microscope described above Functionally, the X-ray measurement of the specific position of the sample is performed, and the X-ray measuring device of the fluorescent X-ray from the measurement sample placed on the substrate can be measured; The line optical element focuses on the optical path of the fluorescent X-ray between the X-ray irradiation position of the cross-sectional area of 50 μm or less and the X-ray detector, and is a structure for suppressing the attenuation of the X-ray of the fluorescent light. Further, in addition to the fact that the measurement sample placed on the substrate includes the same metal element as the substrate, it can be determined that the measurement sample contains the data processing function of the same metal element. unit.

Further, in the present invention, it is preferable that the micro-part X-ray measuring device described above is a fluorescent X-ray between the X-ray irradiation position of the cross-sectional area that is focused and irradiated to the diameter of 50 μm or less and the X-ray detector. The optical path is a vacuum or an optical path of a fluorescent X-ray between the X-ray irradiation position of the cross-sectional area that is focused and irradiated to the 50 μm diameter or less and the X-ray detector, by helium (He). Replacement. Alternatively, the X-ray metal in the X-ray generating device is preferably chromium (Cr) of atomic order 24, molybdenum (Mo) of atomic order 42 to silver (Ag) of atomic order 47, or atomic order 74 a monomer of each element up to the gold (Au) of atomic order 79 or an alloy or a laminated film containing a plurality of elements, vacuum evacuating or helium (He) of the internal space of the aforementioned X-ray optical element Replacement is preferred.

Further, in the above-described micro-part X-ray measuring apparatus, it is preferable that the X-ray detector is configured by a semiconductor X-ray detecting element having an energy discrimination function of one or a plurality of X-ray photons, and further Preferably, the optical microscope has a hole into which the X-ray detecting element can be inserted, and the optical axis of the optical microscope is coaxial with a central axis of the X-ray beam. Further, it is preferable that a reflection optical microscope of a Cassegrain type is used in the optical microscope to align the X-ray beam of the sub-mirror surface of the sample with the coaxial central axis of the optical axis of the optical microscope. The periphery is provided with a singular or plural X-ray detecting element, and further preferably, means for suppressing the divergence angle of the fluorescent X-rays emitted/released by the sample.

According to the present invention, it is possible to provide a microscope image in which a large sample or a sample mounted on a large substrate can be recognized, and an element of a specific minute portion is measured by a fluorescent X-ray, and a substrate (substrate) on which a sample is mounted is provided. The element included in the sample is the same as the element contained in the sample, and the micro-section X-ray measuring device capable of measuring the component of the stable minute portion exhibits an excellent effect in practical use.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[Example 1]

Fig. 1 is a perspective view showing the overall configuration of an X-ray measuring device according to a first embodiment of the present invention. The X-ray generator 1, the X-ray detector 3, and the optical microscope 4 are mounted inside a casing (not shown). The X-ray optical element 2 for focusing the X-ray generated by the X-ray generator 1 on a small area is a polycapillary type element, and the X-ray optical element 2 of the polymerization capillary type is directly mounted on the X-ray optical element 2 X-ray generating device 1. In this way, the X-ray generated by the X-ray generator 1 is focused on a small cross-sectional area of 50 μm or less by the action of the polymeric capillary X-ray optical element 2, and then irradiated onto the sample. Relative to the sample 5 on the moving mechanism (mobile station) 6. Further, the position control of the sample 5 of the X-ray generator 1 and the X-ray irradiation position of the X-ray optical element 2 of the polymerization capillary type is performed by the sample movement control unit 61.

Further, the X-ray optical element 2 of the polymerized capillary type of the present embodiment has the X-ray generating device 1 which generates X-rays using molybdenum (Mo) metal as an X-ray target and focuses X-rays with an energy of 17.5 keV to 15 μm. The diameter of the X-ray of energy 8.0 keV is focused to a diameter of 25 μm. Further, in the X-ray generating device 1 as the metal target in which the X-ray is generated, the aforementioned molybdenum (Mo) of the atomic order 42 may be added to the silver (Ag) of the atomic order 47 or the tungsten of the atomic order 74 (W). Each element up to the gold (Au) of the atomic sequence 79 is used as a monomer or a complex alloy or a laminated film.

Further, the acceleration voltage/current of the X-ray generator 1 and the control of the X-ray shutter and the like are performed by the X-ray generation control unit 11. Further, the confirmation of the irradiation position of the X-ray focused by the above-described polycapillary type X-ray optical element 2 is performed by the optical microscope 4. That is, the light emitted from the microscope light source 43 is irradiated onto the sample 5 by the optical microscope 4, and then the light reflected/scattered by the sample 5 is imaged on the CCD unit 42 mounted on the optical microscope 4 as The sample image is transmitted to the microscope control unit 41 as an electrical signal.

Next, the casing (not shown) is set to the measurement position by freely selecting the position on the ternary coordinate (see X-Y-Z in the drawing) by a position control mechanism (not shown). Here, the quadratic coordinates on the sample 5 of the X-Y substrate, Z is the height of the casing, which is adjusted by the focus position of the substrate and the optical microscope 4.

Next, a more detailed structure of the X-ray measuring apparatus of the first embodiment will be described using the attached FIG. In the sample 5, the X-rays were irradiated by the X-ray generator 1 and the X-ray optical element 2. At this time, the X-ray generated by the X-ray generating device 1 is focused on a small irradiation area by passing through the X-ray optical element 2 as described above. Further, the inside of the X-ray optical element 2 is evacuated or evacuated by helium gas, thereby preventing the X-rays passing through the inside from being attenuated.

On the other hand, the fluorescent X-rays 32 emitted from the minute portion 51 on the sample (substrate) 5 irradiated with the X-rays are captured by the X-ray detector 3, and are converted into the detector control unit 31. The X-ray photon number is sent to the data processing device 7 in a histogram of the fluorescent X-ray energy. Thereby, the X-ray generated by the X-ray generating device 1 is moved to the X-ray optical element 2 by the movement of the sample relative position moving mechanism 6 by the sample 5 captured by the optical microscope 4. The focused/illuminated position causes the fluorescent X-rays generated at this time to be captured by the X-ray detector 3, and the data processing device 7 analyzes the photon energy distribution (spectrum) of the captured fluorescent X-rays, thereby Elemental analysis of the portion where the X-ray is irradiated is performed. In addition, when the distance from the minute portion 51 of the sample to the X-ray detector 3 is 5 mm or less, the characteristic X-ray having an energy of 1.0 keV generated by the minute portion 51 of the sample can be used. This can be detected by suppressing its attenuation in the air.

In particular, in the present embodiment, when molybdenum (Mo) is used as the X-ray target of the X-ray generator 1, the X-ray of 300 Mcps is irradiated to the sample under an operating condition of a voltage of 50 kV and a current of 0.5 mA. The tiny part 51 of 5. At this time, when the metal from the molybdenum (Mo) of the atomic order 42 to the silver (Ag) of the atomic order 47 is an X-ray target, the characteristic X-ray of Lα is mixed into the X-rays to be irradiated. Further, the characteristic X line of Lα is 2.29 keV in MoLα, and the X-ray energy is 2.98 keV in AgLα, that is, near 1.56 keV of the fluorescent X-ray excitation energy of aluminum metal (Al). The fluorescent X-ray of AlKα can be released by aluminum metal (Al) with high efficiency. On the other hand, the characteristic X-rays of MoKα and AgKα are effective for the excitation of the transition metal, and similar to the Al of the metal element generally used, the minute portion of the transition metal of Cr, Fe, Co, Ni, Cu, etc. Line analysis is effective and can be used for high sensitivity measurements.

Next, Fig. 3 shows a flow of coordinate measurement for performing X-ray measurement in the X-ray measuring apparatus of the present invention.

As can be seen from the figure, when the XRF (fluorescence X-ray) measurement position detection is started, the number (m) of the measurement position is first set to m = 0 (step S31), and then the value m is increased by only 1 (m = m + 1) (step S32). Next, the coordinate is moved until the coordinate of the number (m) of the position (for example, (mx, my)) is measured (step S33), and then the Z position is adjusted (step S34). First, optical measurement is performed (step S35), and it is determined whether or not there is the presence of fine particles (step S36). As a result, when it is determined that the presence of fine particles ("Yes" in the figure), the coordinates are recorded (step S37), and thereafter, it is determined whether or not all the measurements are completed by the value of m described above (step S38). On the other hand, when it is determined that no fine particles are present ("No" in the figure), the process proceeds immediately to the above-described step S37.

Next, if the result of the determination in the above step S37 is that the measurement has not been completed ("No" in the figure), the process returns to the above-described step S32, and it is determined that all the measurements are completed ("Yes" in the figure). In the case of the coordinates, the coordinates of the microparticles are placed in front of the recorded coordinates (step S39), and further, M0 = m+1 (step S40), and the processing is terminated.

Further, the above-described flow is for displaying a coordinate for determining the position at which the X-ray measurement is performed, and is performed using visible light. Further, in order to determine the coordinates, in addition to the visible light described above, for example, infrared rays or ultraviolet rays may be used. Further, X-ray measurement can be performed immediately after the X-ray measurement coordinates are determined by visible light.

Further, an example of the photon energy distribution of the fluorescent X-rays measured by the X-ray measuring device having the configuration shown in Figs. 1 and 2 is shown in Figs. 4 to 6 of the drawings. Moreover, in the case of this measurement example, the photon energy of the X-ray generated by the X-ray generator was 5.4 keV.

Fig. 4 is a view showing the energy of the characteristic X-ray of the element contained in the sample, and the measurement data of the photon detected by the measurement for a certain period of time. From the data of Fig. 4, the element contained in the measurement area can be measured. The type and quantity. In the measurement device of the present invention, it is possible to suppress the attenuation of the fluorescent X-rays in the atmosphere by setting the X-ray path in the atmosphere to 5 mm or less. As a result, as shown in FIG. Sodium (Na). Further, since the fluorescent X-ray of calcium (Ca) or barium (Ba) hardly attenuates in the atmosphere, it can be measured under high sensitivity.

Next, a detection method in the case where the substrate contains the same atomic species as the sample microparticles will be described with reference to FIGS. 5 and 6.

A material used as a substrate in most fields is glass. In the related glass, as a general use, there is an alumina silicate having a composition of an alkali metal/alkaline earth metal and a mixture of alumina/yttria. An example of the fluorescent X-ray spectrum of the glass substrate used herein is shown in FIG.

The spectrum shown in Figure 5 is measured for aluminum (Al), cerium (Si), phosphorus (P), a small amount of sulfur (S), chlorine (Cl), and further argon (Ar) in the atmosphere. . Further, from the measurement results, Al and Si were detected as elements contained in the glass. Further, P, S, and Cl were measured by adhering to the surface of the glass.

Here, the Al metal powder is dispersed on the surface of the glass substrate, and the Al metal powder is introduced into the X-ray irradiation region by moving the substrate position, and the fluorescent X-ray is measured under the same conditions as described above. The results obtained thereby are shown in Fig. 6.

Here, when the difference between the measured spectra is taken, a difference spectrum indicating "differential spectrum" is shown in FIG. 7 of the drawing. Further, in this case, the peak appearing is a peak caused by the fine metal powder of Al, that is, a minute foreign matter can be detected. Further, according to this method, the Al minute metal powder of about 1 ng can be detected by the measurement of the apparatus of the present embodiment.

Here, the certainty (confirmability) of the detection of the minute metal powder used in the present invention will be described. The detection of the X-ray is performed by measuring the photon of the X-ray incident on the detector by the detector, and the measurement accuracy of the number (N) is taken as the measurement statistical error (1σ), which is the square root of N. To represent. In addition, in the X-ray measurement, background noise generated by the detector itself or by the electronic circuit is inevitably observed. Next, the measurement intensity of the fluorescent X-rays from the minute foreign matter is represented by a difference (N1 - N0) between the measured value (N1) including the metal fine particles and the measured value (N0) not including the metal fine particles, respectively. The measured value includes the measured statistical error (1σ) of √N1 and √N0. That is, in order to judge that the intensity of the fluorescent X-rays from the fine metal particles is measured at the level of nσ, the following formula (1) is used.

n=(N1-N0)/(√N1+√N0)‧‧‧(1)

At n=1, the normal distribution function has a probability of 68% to determine "the presence of minute metal foreign matter", and the probability is 95% in the case of n=2, and 99.7% in the case of n=3. As an example, when N1 and N0 are 1000 and 900, respectively, n=1.6, and when N1 and N0 are 500 and 400, respectively, n=2.4, even if the measurement intensity (N1-N0) from the minute metal particles is obtained. The same, and because the background fluorescence of the latter is very low, it becomes a highly reliable test. Further, the measured intensity (N1-N0) is the intensity of the fluorescent X-ray derived from the fine metal particles, and is a value roughly proportional to the weight of the metal particles.

Here, when a plurality of types of excessive metal particles are detected, the following processing can be performed to improve the data accuracy. Further, examples of the commonly used transition metal element include chromium (Cr) to atomic order 29 (Cu) of atomic order 24, but among the two types of fluorescent X-rays excited by each element, it is called Kβ. The X-ray on the high energy side overlaps with the spectrum on the low energy side of the atomic order No. 1 called Kα. Its appearance is shown in Figure 8. That is, in the case where the fluorescent X-ray of each element is detected, Kβ is necessarily present in addition to Kα, and processing is performed on the measured spectral data. Similarly, for elements having a larger atomic order, they are treated as a complex number of Lα and Lβ. Thereby, the accuracy of the measurement data can be improved.

Next, a method of suppressing the influence of the elements contained in the substrate using the data of the complex point will be described. The fluorescent X-ray detector used herein uses a so-called energy dispersive type (ED) detector, and the spectrum of the multichannel analyzer is digitally accumulated in the memory of the data processing device 7. That is, the calculations described here are performed at a very high speed.

When there is a plurality of measurement data on the substrate, it is not always necessary to measure the metal microparticles for each measurement point, and the fluorescence X-ray spectrum from the substrate can be estimated. The type of substrate is known. For example, in the case of glass, the composition is an alkali metal (Na, K, etc.), an alkaline earth metal (Ca, Ba, etc.), and aluminum (Al), bismuth (Si), and oxygen (O). In other words, in the case of performing fluorescence X-ray measurement of fine particles, when the fine particles are not transitional metals (for example, Cr, Fe, Co, Ni, Cu, etc.), the elements constituting the fine particles can be judged to be from the source. Fluorescent X-rays of the elements of the substrate. In other words, in the measurement including the fine particles, when the element which is not contained in the original substrate is detected, the fluorescence X-ray spectrum of the element contained in the substrate can be judged to be from the substrate.

For example, when the plurality of metal fine particles are the same as the elements from the substrate, the complex spectrum is compared, for example, the intensity of the fluorescent X-ray corresponding to the spectrum of aluminum (Al) is compared, and the smallest value is assumed to be the fluorescent material derived from the substrate. The X-ray intensity is calculated, and the value of n is calculated by the above formula (1). Similarly, when the n value of the largest Al fluorescent X-ray is equal to or greater than the threshold nt (for example, nt=2.0), the lowest Al-fluorescence X-ray intensity is taken as the fluorescence X-ray intensity from the substrate. As a result, when all of the measured n values are equal to or less than the threshold nt, the intensity of the fluorescent X-ray in the place where the metal fine particles do not exist is taken as the intensity of the fluorescent X-ray from the substrate. In this way, by determining the intensity of the fluorescent X-ray from the substrate, it is always possible to compare the point where the metal fine particles are present, and the measurement of the point where there is no (none), and the measurement can be performed at a high speed. Moreover, an example of the measurement at this time is shown in FIG.

As shown in the flow of FIG. 9 , when the micro-section XRF (fluorescence X-ray) measurement is started, first, the number (m) of the measurement position is set to m=0 (step S91), and then the value m is incremented by only one. (m=m+1) (step S92). Next, the coordinate movement is performed until the coordinate of the number (m) of the measurement position (for example, (mx, my)) (step S93), and then the Z position is adjusted (step S94). Thereafter, XRF (fluorescence X-ray) measurement is performed (step S95), and the minimum value of the m data is found by the data obtained as a result (step S96). Thereafter, k=0 and M1=m are made (step S97), and then k is sequentially incremented by 1 (k=k+1) (step S98), and the total measured n value is calculated (step S99), and the left side of the map is created. The table shown. Thereafter, it is confirmed that all the data processing is completed (steps S100 and S101), and thereafter, the processing is ended.

[Embodiment 2]

10 to 13 show a micro-part X-ray measuring device according to a second embodiment of the present invention. Here, the difference between the micro-X-ray measuring device of the first embodiment described above is mainly Be explained. That is, the micro X-ray measuring device of the second embodiment differs from the micro X-ray measuring device of the first embodiment in that the optical axis of the optical microscope and the X-ray of the sample are irradiated. The axes are consistent. According to the configuration, the individual units of the first embodiment described above can be integrated.

That is, Fig. 10 is a front view showing the micro-part X-ray measuring device of the second embodiment, and Fig. 11 is a side view thereof. 12 and 13 are cross-sectional views in the longitudinal direction and the lateral direction for showing the internal configuration thereof.

As can be seen from these figures, in the micro-section X-ray measuring apparatus of the second embodiment, a Cassegrain mirror is used as an optical microscope. The lens barrel 44 of the Cassegrain-type optical microscope 8 is attached with a CCD unit 42, an optical source 43, and an X-ray generator 1 for observing an optical image of a sample or a sample substrate.

In the micro-section measuring device of the related configuration, the X-ray generated by the X-ray tube 13 is discharged from the X-ray focal point 16 through the X-ray shutter 14 provided inside the X-ray shutter chamber 15, and then through the polymerization capillary. The X-ray optical element 21 is irradiated to the X-ray measurement point 24. At this time, by X-rays of the capillary X-ray optical element 21, the X-ray measurement point 24 is focused by the action of the optical element. Further, the X-ray shutter room 15 occupies most of the path through which the X-ray passes, the polymeric capillary X-ray optical element 21 provided inside the X-ray optical element holding inner tube 22, and the X-ray detector vacuum chamber 35, It is held in a vacuum by exhausting from the vacuum exhaust pipe 25. Thereby, the absorption of the X-ray caused by the air is suppressed.

The X-rays generated at the X-ray measurement points are incident on the X-ray detecting elements 33 provided inside the X-ray detector vacuum chamber 35 through the X-ray transmission window 23, and are converted into electric signals, which are transmitted through FIG. A signal line (not shown) is input to the detector control unit 31, and then a fluorescence X-ray spectrum is obtained in the data processing device 7.

On the other hand, the visible light emitted by the microscope light source 43 is reflected by the crucible 45 while being passed by the Cassegrain type optical microscope 8, by the Cassegrain pair disposed on the sub mirror holding rod 83. The mirror 82 and the Cassegrain main mirror 81 reflect the focus, and are focused/illuminated to the X-ray measuring point 24 like the X-ray. The optical image of the measurement point 24 is projected onto the CCD unit 42 by the Cassegrain sub-mirror 82, the Cassegrain main mirror 81, and the crucible 47.

Hereinafter, the arrangement of the X-ray detecting elements 34 inside the X-ray detector vacuum chamber 35 will be described in detail with reference to FIG.

In the central portion of the X-ray detector vacuum chamber 35, a capillary X-ray optical element 21 is disposed, and an X-ray detecting element 34 is mounted around the capillary X-ray optical element 21. In the present embodiment, an example in which four X-ray detecting elements are mounted is shown. The number of the X-ray detecting elements is determined by the intensity of the fluorescent X-rays assumed in advance, and then the X-ray transmitting window 23 of the beryllium (Be, beryllium) foil and the X-ray detector vacuum chamber 35 are used, for example, Sealed by welding or bonding, the polymeric capillary X-ray optical element 21 and the X-ray detector vacuum chamber 35 are evacuated by vacuum and held in a vacuum. Thereby, the absorption of the X-rays by the air in the portion of the X-ray transmission window 23 and the X-ray detecting element 34 among the paths of the fluorescent X-rays generated by the sample is suppressed.

Further, in the outer peripheral portion of the X-ray detector vacuum chamber 35, a visible light transmission window 26 is provided, and the optical path of the imaging optical system for illumination and observation of the sample image is formed. Since the axis of the X-ray to be irradiated coincides with the optical axis of the observation microscope, the position of the visible light focus and the X-ray focus can be fixed by adjustment during the manufacture of the device, so that it can be easily provided or adjusted. The advantages of the tiny part X-ray measuring device.

[Example 3]

Fig. 14 shows a micro-part X-ray measuring device according to a third embodiment of the present invention. Here, the difference from the micro-part X-ray measuring device of the second embodiment described above is mainly performed. Description. That is, the micro-X-ray measuring device shown in FIG. 14 is different from the Cassegrain-type optical microscope used in the micro-X-ray measuring device of the second embodiment, by the central optical axis of the refractive lens. A hole is partially opened, and the polymeric capillary X-ray optical element 21 is mounted there, and the optical system for sample observation is aligned with the axis of the sample irradiated to the X-ray optical system. Further, according to the configuration described above, the detection of the fluorescent X-rays is different from the above-described second embodiment, and is disposed as a separate unit around the objective lens 48. That is, in the third embodiment, the X-rays incident on the detector are taken in by the polymerization capillary X-ray optical element 37 on the incident side of the X-ray detector of the fluorescent X-ray detector 36. The solid angle is increased, and thus, a device capable of performing high-sensitivity measurement is realized.

Even in the present embodiment, the X-ray optical element holds the inner tube 22 and the fluorescent X-ray optical element in the inside of the inner tube 38, and is evacuated or replaced by helium gas, thereby preventing passage through the inside of these. The X-ray attenuation inside the polymeric capillary X-ray optical element 21 and the polymeric capillary fluorescent X-ray optical element 37.

1. . . X-ray generating device

2. . . X-ray optics

3. . . X-ray detector

4. . . Optical microscope

5. . . Sample, sample plate

6. . . Specimen relative moving mechanism

7. . . Data processing device

8. . . Cassegrain optical microscope

11. . . X-ray generation control unit

12. . . X-ray tube shelter

13. . . X-ray tube

14. . . X-ray shutter

15. . . X-ray shutter room

16. . . X-ray focus

17. . . Sample irradiation X-ray

twenty one. . . Polycapillary X-ray optics

twenty two. . . X-ray optical component holding lens barrel

twenty three. . . X-ray transmission window

31. . . Detector control unit

32. . . Fluorescent X-ray

34. . . X-ray detecting element

35. . . X-ray detection vacuum chamber

36. . . Fluorescent X-ray detector

37. . . Polycapillary fluorescent X-ray optics

38. . . Fluorescent X-ray optics keep the lens barrel

41. . . Microscope control department

42. . . CCD unit

43. . . Microscope light source

44. . . Lens barrel

45. . .稜鏡

48. . . Objective lens

51. . . Sample

61. . . Sample movement control unit

81. . . Cassegrain main mirror

82. . . Cassegrain sub mirror

83. . . Secondary mirror retaining rod

Fig. 1 is a perspective view showing a schematic configuration of a micro-section X-ray measuring apparatus according to a first embodiment of the present invention.

Fig. 2 is a view for explaining measurement of fluorescent X-rays from a sample of the micro-part X-ray measuring device of the first embodiment.

Fig. 3 is a view showing a flow of coordinates of a sample position for determining the X-ray measurement by the micro-section X-ray measuring device of the first embodiment.

4 is a measurement example of the measurement example (measurement example 1) of the sample on the glass substrate measured by the X-ray generation device (X-ray tube) of the chromium (Cr) target, which is the micro-section X-ray measuring device of the first embodiment. A diagram of the X-ray spectrum.

Fig. 5 is a view showing another measurement example (measure example 3) of the sample on the glass substrate measured by the X-ray generating device (X-ray tube) of the chromium (Cr) target using the micro-section X-ray measuring device of the first embodiment; Contains a map of the X-ray spectrum.

6 is a micro-section X-ray measuring apparatus according to the first embodiment, which measures a sample on a glass substrate having aluminum micro-metal powder on the surface thereof using an X-ray generating device (X-ray tube) of a chromium (Cr) target. The measurement example (measurement example 3) contains the X-ray spectrum.

Fig. 7 is a view showing the measurement example 2 and the measurement example 3 measured by the X-ray generation device (X-ray tube) using a chromium (Cr) target, and the inclusion of the difference therebetween, in the micro-section X-ray measuring device according to the first embodiment. A diagram of the X-ray spectrum.

Fig. 8 is a view showing an example of Kα and Kβ spectra of transition metal elements from chromium (Cr) of atomic order 24 to copper (Cu) of atomic order 29.

Fig. 9 is a view showing a flow of micro-section XRF (fluorescence X-ray) measurement in the case where the measurement target has a plurality of points in the micro-section X-ray measuring device according to the first embodiment.

Fig. 10 is a front elevational view showing a micro-part X-ray measuring apparatus according to a second embodiment of the present invention.

Fig. 11 is a side view showing a micro-part X-ray measuring apparatus according to a second embodiment of the present invention.

Fig. 12 is a longitudinal cross-sectional view showing the configuration of an X-ray and a visible light optical system of the micro-part X-ray measuring device according to the second embodiment.

Fig. 13 is a transverse cross-sectional view showing the configuration of the X-ray and visible light optical system of the micro-part X-ray measuring device of the second embodiment.

Fig. 14 is a longitudinal cross-sectional view showing the internal structure of a micro-section X-ray measuring apparatus according to a third embodiment of the present invention.

1. . . X-ray generating device

2. . . X-ray optics

3. . . X-ray detector

4. . . Optical microscope

5. . . Sample, sample plate

7. . . Data processing device

17. . . Sample irradiation X-ray

31. . . Detector control unit

32. . . Fluorescent X-ray

42. . . CCD unit

43. . . Microscope light source

51. . . Sample

Claims (3)

A micro-section X-ray measuring device includes: an X-ray generating device that detects an X-ray optical element that is focused on a measurement sample by a X-ray emitted by the X-ray generating device and has a cross-sectional area of 50 μm or less in diameter; The X-ray detector of the fluorescent X-ray emitted from the measurement sample, the optical microscope capable of capturing the optical image of the X-ray irradiation position, and the second measurement of the measurement sample can be positioned, and can be positioned in the height direction. a sample relative movement mechanism for adjusting the position thereof; and a micro X-ray measuring device for measuring a fluorescent X-ray from the measurement sample placed on the substrate; wherein the X-ray optical element and the X-ray are The detector is held in a vacuum or helium (He) by the X-ray detector vacuum chamber, and has an X-ray transmission window that transmits the X-ray of the helium or vacuum, and is focused and irradiated to a diameter of 50 μm or less. The X-ray irradiation position of the sectional area can be moved to a specific position by the image recognition function of the optical microscope, and the interval between the X-ray transmission window and the irradiation position of the X-ray can be set to 5 mm or less. Further, the measurement data including the measurement statistical error including only the substrate is measured, and the measurement data including the measurement statistical error from the measurement sample placed on the substrate is measured, and both of them are taken. The difference between the measurement data, even if the measurement sample placed on the substrate includes the same metal element as the substrate, it can be determined that the measurement sample contains a data processing unit having a data processing function of the same metal element; wherein the X-ray detector is composed of one or a plurality of X-ray detectors, and the one or more X-ray detectors are housed in individual vacuum chambers, and have 1 The semiconductor X-ray detecting element of the energy discrimination function of the plurality of X-ray photons; wherein the optical microscope has a hole into which the X-ray optical element can be inserted, and the light of the optical microscope The axis is coaxial with the central axis of the X-ray beam, and the X-ray detecting element is provided around the central axis of the optical microscope; and the Cassegrain-type reflection optical microscope is used in the optical microscope to measure the opposite direction. On the back side of the sub-mirror of the sample, there are singular or plural X-ray detecting elements. The micro-section X-ray measuring device according to claim 1, wherein the X-ray optical element has one or a plurality of semiconductor X-ray detecting elements, and is vacuum-exhausted together with the X-ray optical element. An x-ray detector is provided in the same vacuum chamber in which helium (He) is replaced, and the X-ray generator is opposed to the surface of the vacuum chamber of the measurement sample placed in the atmosphere before the X-ray optical element. All or part of it has an X-ray window that passes through the X-ray. The micro-section X-ray measuring device according to claim 1 or 2, wherein the X-ray metal in the X-ray generating device is a chromium (Cr) of atomic order 24 and a molybdenum (Mo) atom of atomic order 42. Monomer of each element of silver (Ag) of order 47 or tungsten (W) of atomic order 74 to gold (Au) of atomic order 79 or alloy or layer containing plural elements membrane.