Combined detection system of X-ray absorption spectrum, detection method and application

Abstract

The invention discloses a combined detection system and detection method for an X-ray absorption spectrum and application, and the combined detection system for the X-ray absorption spectrum is characterized in that an X-ray excitation source is arranged right above a to-be-detected sample and can emit X-rays to vertically irradiate a position A of the sample; the X-ray detector is positioned right below the sample A and is used for detecting an X-ray signal after penetrating through the sample; meanwhile, different to-be-measured optical signals can be excited at the position A of the sample, and the to-be-measured optical signals are emitted in different directions close to one side of the sample; the optical fiber coupling optical path module is connected with the spectrograph, is located at different positions above the sample and is used for collecting optical signals to be measured and transmitting the optical signals to be measured to the spectrograph for detection; when the optical fiber coupling light path module is located under the X-ray excitation source, a through hole is formed in the optical fiber coupling light path module and used for allowing X-rays to pass through, and therefore the X-rays transmitted at the position A of the sample and excited to-be-measured light signals at the position A are detected at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of X-ray absorption spectrum detection, and more particularly to a combined detection system, detection method and application of X-ray absorption spectrum. Background Art

[0002] X-ray absorption spectroscopy is an important material characterization technique. By analyzing the absorption characteristics of a substance to X-rays, information such as the chemical state, coordination structure, and electronic state of the substance's elements can be obtained. It is widely used in catalysis, energy materials, environmental science, and other fields. Traditional X-ray absorption spectroscopy systems usually rely on synchrotron radiation sources or laboratory X-ray sources, combined with X-ray detectors (such as ionization chambers and silicon drift X-ray detectors) to obtain absorption signals. However, a single X-ray absorption spectroscopy technique is difficult to fully analyze the multi-scale dynamic changes of materials in complex reaction processes, such as the generation and recombination of electron-hole pairs in photocatalytic reactions, the evolution of surface defect states, etc., and it is urgently needed to be combined with other spectroscopic techniques (such as fluorescence spectroscopy, Raman spectroscopy, and infrared reflectance spectroscopy) to achieve in-situ multi-dimensional information acquisition. Summary of the Invention

[0003] This solution provides a combined detection system, detection method and application of X-ray absorption spectrum. When performing X-ray absorption spectrum detection, the system can be combined with other spectral signal detection to obtain multi-dimensional information of the sample.

[0004] In order to achieve the above object, the technical solution provided by the present invention is:

[0005] An X-ray absorption spectrum combined detection system includes an X-ray excitation source, a fiber-coupled optical path module and an X-ray detector;

[0006] The X-ray excitation source is arranged directly above the sample to be detected and is capable of emitting X-rays vertically toward point A of the sample; the X-ray detector is located directly below point A of the sample and is used to detect X-ray signals after passing through the sample;

[0007] At the same time, point A of the sample can be excited to produce a light signal to be measured, and the light signal to be measured is emitted in different directions close to one side of the sample; the fiber-optic coupling optical path module is connected to the spectrometer and is located at different positions above the sample to collect the light signal to be measured, and transmit the light signal to be measured to the spectrometer for detection; when the fiber-optic coupling optical path module is located directly below the X-ray excitation source, a through hole is opened on the fiber-optic coupling optical path module for X-rays to pass through.

[0008] As a further improvement, the light signal to be measured excited on the sample is generated when the X-rays emitted by the X-ray excitation source irradiate the sample.

[0009] As a further improvement, it further includes an ultraviolet-visible-infrared band excitation source, and the ultraviolet-visible-infrared band excitation source is connected to the fiber-coupled optical path module;

[0010] The optical signal to be measured excited on the sample is generated by the optical signal emitted by the ultraviolet-visible-infrared band excitation source and focused by the optical fiber coupling optical path module and irradiated onto the sample.

[0011] As a further improvement, the fiber-coupled optical path module is an off-axis parabolic mirror probe, which includes an off-axis parabolic mirror arranged at one end of the off-axis parabolic mirror probe and an achromatic lens located inside the off-axis parabolic mirror probe; the off-axis parabolic mirror is located directly below the X-ray excitation source, and the through hole is opened on the off-axis parabolic mirror; the off-axis parabolic mirror is facing the side of the sample, and an opening is opened on the off-axis parabolic mirror probe.

[0012] As a further improvement, the fiber-coupled optical path module is a plane mirror probe, which includes a plane mirror arranged at one end of the plane mirror probe and a plane mirror post-achromatic lens and a plane mirror pre-achromatic lens located inside the plane mirror probe, and the plane mirror pre-achromatic lens is arranged at one end close to the plane mirror; the plane mirror is located directly below the X-ray excitation source, and the through hole is opened on the plane mirror; the plane mirror is facing the sample side, and an opening is opened on the plane mirror probe.

[0013] As a further improvement, the fiber-coupled optical path module is an objective lens probe, which is single-sided or double-sided; the objective lens probe is tilted and located at the oblique side of the X-ray irradiation path, and the objective lens probe includes a front lens and a rear lens respectively arranged near its two ends; the objective lens probe has an opening at one end facing the sample.

[0014] As a further improvement, the through hole has a diameter of 1-10 mm.

[0015] As a further improvement, the optical signal to be measured includes one of a scintillator fluorescence signal, a Raman light signal, a photoluminescence signal and an infrared reflectance spectrum light signal.

[0016] The present invention also provides a detection method of a combined detection system of X-ray absorption spectrum,

[0017] The X-ray excitation source is placed directly above the sample to be inspected and is capable of emitting X-rays vertically toward point A of the sample;

[0018] The X-ray detector is positioned directly below the sample to detect X-ray signals passing through the sample;

[0019] At the same time, the sample A is excited to generate a light signal to be measured, and the light signal to be measured is emitted in different directions close to one side of the sample;

[0020] Connecting the fiber-coupled optical path module to a spectrometer and setting it at different positions above the sample to collect the optical signal to be measured, and transmitting the optical signal to be measured to the spectrometer for detection;

[0021] When the fiber-coupled optical path module is located directly below the X-ray excitation source, a through hole is provided on the fiber-coupled optical path module for X-rays to pass through.

[0022] The present invention also provides an application of a combined detection system for X-ray absorption spectrum, including the combined detection system for X-ray absorption spectrum, which simultaneously detects the X-rays transmitted at point A of the sample and the light signal to be measured excited at that point, for multi-scale analysis of the sample material to be detected.

[0023] The technical solution provided by the present invention has the following beneficial effects compared to the existing technology: This solution uses an X-ray excitation source to emit X-rays toward a sample, and simultaneously stimulates different light signals to be measured at the same location on the sample. On the one hand, the X-ray detector receives the spectrum of the rays after passing through the sample and analyzes the absorption characteristics of the sample material to obtain information such as the chemical state, coordination structure, and electronic state of the sample material elements. On the other hand, the optical fiber coupling optical module can also be used to analyze the spectral information of the light signal to be measured in situ, simultaneously detecting the X-rays transmitted at location A of the sample and the light signal to be measured excited at that location. At the same time, other changes in the sample material can be analyzed to obtain more characteristic information, such as the generation and recombination of electron-hole pairs in the material and the evolution of defect states on the sample surface, thereby realizing in situ multi-dimensional and multi-scale information acquisition. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the sample being irradiated by the excitation source;

[0025] Figure 2 It is a schematic diagram of the off-axis parabolic mirror probe structure;

[0026] Figure 3 Schematic diagram of the plane reflector probe structure;

[0027] Figure 4 This is the principle diagram of the optical fiber coupling optical path module collecting optical signals for the off-axis parabolic mirror probe;

[0028] Figure 5 This is the principle diagram of the optical fiber coupling optical path module collecting optical signals for the plane reflector probe;

[0029] Figure 6 This is the principle diagram of the fiber-coupled optical path module collecting light signals for a single-side objective lens probe;

[0030] Figure 7 This is the basic structure diagram of the fiber-coupled optical path module as a probe with double-sided emission and collection lens separation;

[0031] Figure 8 This is a diagram of scintillator fluorescence measurement when the fiber-coupled optical path module is an off-axis parabolic mirror probe;

[0032] Figure 9 This is a diagram of scintillator fluorescence measurement when the fiber-coupled optical path module is a plane reflector probe;

[0033] Figure 10 This is a diagram of scintillator fluorescence measurement when the fiber-coupled optical path module is a single-sided objective lens probe;

[0034] Figure 11 This is a diagram of scintillator fluorescence measurement when the fiber-coupled optical path module is a double-sided objective lens probe;

[0035] Figure 12 This is a diagram of the application of Raman or photoluminescence measurement when the fiber-coupled optical path module is an off-axis parabolic mirror probe;

[0036] Figure 13 This is a diagram of Raman or photoluminescence measurement when the fiber-coupled optical path module is a plane mirror probe;

[0037] Figure 14 This is a diagram of a fiber-coupled optical path module used for Raman or photoluminescence measurement when it is a single-sided objective lens probe.

[0038] Figure 15 This is a diagram of a fiber-coupled optical path module used for Raman or photoluminescence measurement when it is a double-sided objective lens probe.

[0039] Figure 16 This is the infrared reflection spectrum measurement diagram when the fiber-coupled optical path module is an off-axis parabolic mirror probe;

[0040] Figure 17 It is used in infrared reflection spectrum measurement when the fiber-optic coupling optical path module is a plane reflector probe;

[0041] Figure 18 This diagram shows the application of the fiber-coupled optical path module as a double-sided objective lens probe in infrared reflection spectrum measurement.

[0042] Description of labels:

[0043] 1. X-ray excitation source; 2. Sample; 3. Photoluminescence signal; 4. Raman signal; 5. Scintillator fluorescence signal; 6. X-ray detector; 7. Off-axis parabolic mirror; 8. Through hole;

[0044] 13. Single-sided objective lens front lens; 14. Single-sided objective lens sleeve; 15. Single-sided objective lens rear lens; 16. Single-sided objective lens fiber adapter; 17. Second single-sided objective lens front lens; 18. Second single-sided objective lens sleeve; 19. Second single-sided objective lens rear lens; 20. Second single-sided objective lens fiber adapter;

[0045] 28. Achromatic lens; 29. ​​Off-axis parabolic mirror fiber adapter;

[0046] 32. Ultraviolet-visible-infrared band excitation source; 33. First converging lens; 34. Dichroic mirror; 35. Long-wave pass filter; 36. Second converging lens; 37. First spectrometer; 388. Band-pass filter;

[0047] 38. Plane reflector; 39. Plane reflector holder;

[0048] 40. Plane mirror fiber adapter; 41. Plane mirror rear achromatic lens; 42. Plane mirror front achromatic lens; 43. Plane mirror lens sleeve; 44. Second spectrometer; 45. Third spectrometer;

[0049] 50. Fourth spectrometer; 51. Second ultraviolet-visible-infrared band excitation source; 52. Fiber combiner. DETAILED DESCRIPTION

[0050] In order to further understand the content of the present invention, the present invention is described in detail with reference to the accompanying drawings and embodiments.

[0051] The structures, proportions, sizes, etc. depicted in the drawings of this specification are only used to match the contents disclosed in the specification so as to facilitate understanding and reading by persons familiar with this technology. They are not intended to limit the conditions under which the present invention can be implemented and therefore have no substantive technical significance. Any structural modifications, changes in proportional relationships, or adjustments in size should still fall within the scope of the technical contents disclosed in the present invention without affecting the effects and objectives that can be achieved by the present invention.

[0052] It should be noted that the terms "first," "second," and the like in the specification and claims of this application and the accompanying drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or precedence. It should be understood that the terms used in this manner are interchangeable where appropriate, for the purposes of describing the embodiments of the present application herein.

[0053] In the present application, the terms "upper", "lower", "left", "right", "front", "back", "top", "bottom", "inside", "outside", "middle", "vertical", "horizontal", "transverse", "longitudinal" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings. These terms are mainly intended to better describe the present application and its embodiments, and are not intended to limit the indicated devices, elements or components to having a specific orientation, or to be constructed and operated in a specific orientation. Moreover, in addition to being used to indicate orientations or positional relationships, some of the above terms may also be used to indicate other meanings. For example, the term "upper" may also be used to indicate a certain dependency or connection relationship in certain circumstances. For those of ordinary skill in the art, the specific meanings of these terms in the present application can be understood according to the specific circumstances.

[0054] Combine Figure 1-7 As shown, this embodiment provides an X-ray absorption spectrum combined detection system, including an X-ray excitation source 1, a fiber-coupled optical path module and an X-ray detector 6.

[0055] like Figure 1 As shown, an X-ray excitation source 1 is positioned directly above a sample 2 to be tested and is capable of emitting X-rays vertically toward point A of the sample 2. An X-ray detector 6 is located directly below point A of the sample 2 and is used to detect X-ray signals after passing through the sample 2. At the same time, point A of the sample 2 can be excited to produce different optical signals to be measured, which are emitted in different directions near the side of the sample 2. A fiber-coupled optical path module is connected to a spectrometer and is located at different positions above the sample 2 to collect the optical signals to be measured and transmit them to the spectrometer for detection. When the fiber-coupled optical path module is located directly below the X-ray excitation source 1, a through hole 8 is provided on the fiber-coupled optical path module for the X-rays to pass through.

[0056] In this solution, when the X-ray transfers energy to point A on the surface of the sample 2, a scintillator fluorescence signal 5 can also be simultaneously excited from the surface of the sample 2 as a light signal to be measured. The scintillator fluorescence signal 5 propagates in different directions. On the one hand, the X-ray spectrum after passing through the sample 2 is received by the X-ray detector 6, and the absorption characteristics of the sample 2 material to X-rays are analyzed to obtain information such as the chemical state, coordination structure and electronic state of the elements of the sample 2 material. On the other hand, the spectral information of the light signal to be measured can be analyzed in situ through the fiber-optic coupling optical path module, and other changes in the sample 2 material can be analyzed at the same time to obtain more characteristic information, such as the generation and recombination of electron-hole pairs in the material, the evolution of defect states on the sample surface, etc., to achieve in-situ multi-dimensional information acquisition.

[0057] It should be noted that the excitation of the optical signal to be measured can be by X-ray excitation or other optical signals. In one case, the optical signal to be measured excited on sample 2 is simultaneously excited when X-rays emitted by X-ray excitation source 1 irradiate sample 2. For example, if the optical signal to be measured is a scintillator fluorescence signal 5, the scintillator fluorescence signal 5 is simultaneously excited when X-rays emitted by X-ray excitation source 1 irradiate sample 2.

[0058] In another embodiment, the system further includes an ultraviolet-visible-infrared (UV-VIS-IR) excitation source connected to a fiber-coupled optical module. The optical signal to be measured, excited on sample 2, is generated by the optical signal emitted by the UV-VIS-IR excitation source, which is focused by the fiber-coupled optical module and irradiated onto sample 2. For example, when the optical signal to be measured is a Raman light signal 4, a photoluminescence signal 3, or an infrared reflectance spectrum light signal, when X-rays irradiate point A of sample 2, the optical signal emitted by the UV-VIS-IR excitation source is simultaneously focused by the fiber-coupled optical module and irradiated onto point A of sample 2, thereby generating the desired optical signal to be measured. For example, the UV-VIS-IR excitation source emits a laser signal.

[0059] like Figure 2 and Figure 4 As shown, in one embodiment, the fiber-coupled optical path module is an off-axis parabolic mirror probe, which includes an off-axis parabolic mirror 7 disposed at one end of the off-axis parabolic mirror probe and an achromatic lens 28 located within the off-axis parabolic mirror probe. The off-axis parabolic mirror 7 is located directly below the X-ray excitation source 1, and a through hole 8 is defined in the off-axis parabolic mirror 7.

[0060] Specifically, the off-axis parabolic mirror probe also includes an off-axis parabolic mirror lens sleeve, the achromatic lens 28 is arranged in the off-axis parabolic mirror lens sleeve, the off-axis parabolic mirror 7 is installed at one end of the off-axis parabolic mirror lens sleeve, and the off-axis parabolic mirror fiber optic adapter 29 is installed at the other end of the off-axis parabolic mirror lens sleeve.

[0061] When the off-axis parabolic mirror probe is in use, X-rays pass through through-hole 8 and strike a specific point on the surface of sample 2, which serves as the focal point of off-axis parabolic mirror 7. The optical signal to be measured, collected by off-axis parabolic mirror 7, is reflected as parallel light by off-axis parabolic mirror 7. This light is then focused by achromatic lens 28 and enters off-axis parabolic mirror fiber adapter 29, where it is input via optical fiber to second spectrometer 44. The focal point of achromatic lens 28 corresponds to the center of the optical adapter. The wavelength of the optical signal to be measured varies depending on the sample being measured. Using an achromatic lens ensures that the focal point of light of different wavelengths converges to a roughly uniform point, maintaining a constant distance between the achromatic lens and the fiber adapter.

[0062] like Figure 3 and Figure 5 As shown, in one case, the fiber-coupled optical path module is a plane mirror probe, which includes a plane mirror 38 arranged at one end of the plane mirror probe and a plane mirror post-achromatic lens 41 and a plane mirror pre-achromatic lens 42 located inside the plane mirror probe, wherein the plane mirror pre-achromatic lens 42 is arranged at one end close to the plane mirror 38; the plane mirror 38 is located directly below the X-ray excitation source 1, and the through hole 8 is opened on the plane mirror 38.

[0063] Specifically, the plane reflector probe further includes a plane reflector lens sleeve 43, one end of which is provided with a plane reflector holder 39, on which the plane reflector 38 is mounted, and the other end of the plane reflector lens sleeve 43 is provided with a plane reflector fiber adapter 40, and a plane reflector post-achromatic lens 41 is provided near one end of the plane reflector fiber adapter 40. It should be noted that the through hole 8 needs to pass through both the plane reflector 38 and the plane reflector holder 39.

[0064] The arrangement of the plane reflector post-achromatic lens 41 and the plane reflector pre-achromatic lens 42 can realize 4f imaging, so that the formed image can be accurately converged at the center of the optical fiber adapter.

[0065] When the plane mirror probe is in use, X-rays pass through through-hole 8 and strike the surface of sample 2. The light signal to be measured is reflected by plane mirror 38 to plane mirror pre-achromatic lens 42. This pre-achromatic lens 42 converts the reflected light into parallel light. The post-achromatic lens 41 focuses the light into plane mirror fiber adapter 40, where it is input via optical fiber to second spectrometer 44. Unlike an off-axis parabolic mirror probe, the plane mirror reflection probe eliminates the aberration problem caused by the off-axis parabolic mirror.

[0066] In one embodiment, the fiber-coupled optical path module is an objective lens probe, which is single-sided or double-sided. The objective lens probe is tilted and located obliquely to the side of the X-ray irradiation path, and includes a front lens and a rear lens respectively disposed near its two ends.

[0067] Specifically, if Figure 6 As shown, the fiber-coupled optical path module is a single-sided objective probe, which includes a single-sided objective lens sleeve 14, and a single-sided objective lens front lens 13 and a single-sided objective lens rear lens 15 located within the single-sided objective lens sleeve 14. The single-sided objective lens sleeve 14 is open at one end, and a single-sided objective fiber adapter 16 is mounted at the other end. The single-sided objective lens front lens 13 is located near the open end of the single-sided objective lens sleeve 14, and the single-sided objective lens rear lens 15 is located near one end of the single-sided objective fiber adapter 16.

[0068] Only one single-sided objective probe is used, located on one side of the X-ray path and at a 45° angle to both the X-ray path and the sample surface. The single-sided objective front lens 13 and single-sided objective rear lens 15 achieve 4f imaging, meaning the optical field between the image plane and the object plane is 1:1. These lenses, composed of two sets of achromatic lenses, also achieve 4f imaging, ultimately converging on the optical fiber through the single-sided objective fiber adapter 16.

[0069] like Figure 7 As shown, the fiber-coupled optical path module is a double-sided objective lens probe, that is, it is composed of two single-sided objective lens probes. The two single-sided objective lens probes have the same structure and can detect the optical signals to be measured on both sides of the X-ray irradiation path. Specifically, the other objective lens probe includes a second single-sided objective lens pre-lens 17, a second single-sided objective lens lens sleeve 18, a second single-sided objective lens rear lens 19, and a second single-sided objective lens fiber adapter 20; wherein the second single-sided objective lens pre-lens 17 corresponds to the single-sided objective lens pre-lens 13, the second single-sided objective lens lens sleeve 18 corresponds to the single-sided objective lens lens sleeve 14, the second single-sided objective lens rear lens 19 corresponds to the single-sided objective lens rear lens 15, and the second single-sided objective lens fiber adapter 20 is connected to the single-sided objective lens fiber adapter 16.

[0070] When using a dual-lens probe, the two objective lenses are symmetrically positioned on either side of the X-ray path, with the two lens tubes forming a 45° angle with the X-ray path. In one scenario, when using a dual-lens probe, one of the probes can also be used to emit excitation light. Its optical fiber is connected to an external UV-Vis-Infrared excitation source, while the other probe is connected to an external spectrometer.

[0071] As a further improvement, the aperture of the through hole 8 is in the millimeter range, specifically 1-10 mm, to avoid blocking the X-ray irradiation.

[0072] The fiber-coupled optical path modules are all connected to the optical fiber through a fiber adapter. The diameter of the optical fiber must be larger than the diameter of the light spot focused by the probe to ensure that the light is completely collected into the optical fiber and to ensure the reliability of the collected light wave intensity.

[0073] In addition, the present application also provides a detection method of a combined detection system of X-ray absorption spectrum. Specifically, an X-ray excitation source 1 is set directly above the sample 2 to be detected and can emit X-rays vertically to point A of the sample 2;

[0074] The X-ray detector 6 is positioned directly below the sample 2 to detect the X-ray signal after passing through the sample 2;

[0075] At the same time, the sample 2A can be stimulated to generate a light signal to be measured, and the light signal to be measured is emitted in different directions close to the side of the sample 2;

[0076] Connect the fiber-coupled optical path module to the spectrometer and set it at different positions above the sample 2 to collect the light signal to be measured, and transmit the light signal to be measured to the spectrometer for detection;

[0077] When the fiber-coupled optical path module is located directly below the X-ray excitation source 1 , a through hole 8 is provided on the fiber-coupled optical path module for X-rays to pass through.

[0078] A detection method for a combined detection system of X-ray absorption spectrum can perform multi-scale analysis on the material by simultaneously detecting the X-rays transmitted through point A of the sample 2 and the light signal to be measured excited at the point.

[0079] Therefore, the present application also provides an application of a combined detection system for X-ray absorption spectrum, including the combined detection system for X-ray absorption spectrum, which simultaneously detects the X-rays transmitted at point A of sample 2 and the light signal to be measured excited at that point, for multi-scale analysis of the sample 2 material to be detected.

[0080] In order to better understand the content of this application, the application will be further explained in detail below with different embodiments.

[0081] Example 1

[0082] In this embodiment, an X-ray absorption spectrum combined detection system is used to detect the scintillator fluorescence signal and simultaneously analyze the X-ray absorption of sample 2, thereby analyzing and judging sample 2, and performing multi-scale analysis of the sample 2 material.

[0083] Specific detection methods, such as Figure 8 The figure shows a specific example of using an off-axis parabolic mirror probe to detect scintillator fluorescence. The off-axis parabolic mirror probe is positioned above sample 2, with the off-axis parabolic mirror lens sleeve parallel to the surface of sample 2. The off-axis parabolic mirror 7 is positioned directly above sample 2. X-rays pass through through-hole 8, through the off-axis parabolic mirror 7, and into sample 2, stimulating scintillator fluorescence. This excited scintillator fluorescence is collected by the off-axis parabolic mirror 7 and converted into parallel light. This light is then converged by an achromatic lens 28 and passed through the off-axis parabolic mirror fiber adapter 29 to an optical fiber, ultimately connecting to a second spectrometer 44 for measurement. Simultaneously, the X-rays that pass through sample 2 are received by an X-ray detector 6, which measures its X-ray absorption spectrum.

[0084] like Figure 9The figure shows a specific example of using a plane mirror probe to detect scintillator fluorescence. The plane mirror probe is positioned above sample 2, with plane mirror lens sleeve 43 parallel to the surface of sample 2 and plane mirror 38 positioned directly above sample 2. X-rays pass through through-hole 8, through plane mirror 38, and into sample 2, stimulating scintillator fluorescence. This is reflected by the plane mirror, then converted to parallel light by plane mirror pre-achromatic lens 42. After being converged by plane mirror post-achromatic lens 41, the light passes through plane mirror fiber adapter 40 and is finally connected to a second spectrometer 44 for measurement. Simultaneously, the X-rays passing through sample 2 are received by X-ray detector 6, and its X-ray absorption spectrum can be measured.

[0085] like Figure 10 The figure shows a specific example of using a single-sided objective probe to detect scintillator fluorescence. The single-sided objective probe is positioned above sample 2 and tilted, with one end of the single-sided objective lens barrel 14 facing toward sample 2. X-rays incident on sample 2 excite scintillator fluorescence, which then enters through the opening of the single-sided objective lens barrel 14. After being converted into parallel light by the single-sided objective front lens 13, it is converged by the single-sided objective rear lens 15, passes through the single-sided objective fiber adapter 16, and finally connects to the second spectrometer 44 for measurement. Simultaneously, the X-rays passing through the sample 2 are received by the X-ray detector 6, and its X-ray absorption spectrum can be measured.

[0086] like Figure 11 A specific example of using a double-sided objective lens probe to detect scintillator fluorescence is given. Two single-sided objective lens probes are located on either side of the electromagnetic wave signal illumination path. X-rays incident on sample 2 excite the scintillator fluorescence, which is converted into parallel light by a single-sided objective lens front lens 13 and then converged by a single-sided objective lens rear lens 15. It then passes through a single-sided objective lens fiber adapter 16 to an optical fiber and is finally connected to a third spectrometer 45 for measurement. The scintillator fluorescence on the other side is converted into parallel light by a second single-sided objective lens front lens 17 and then converged by a second single-sided objective lens rear lens 19. It then passes through a second single-sided objective lens fiber adapter 20 to an optical fiber and is finally connected to a second spectrometer 44 for measurement. Simultaneously, the X-rays passing through the sample 2 to be tested are received by an X-ray detector 6, and its X-ray absorption spectrum can be measured.

[0087] Example 2

[0088] In this embodiment, a combined detection system of X-ray absorption spectrum is used to detect Raman light signals, and at the same time, the X-ray absorption of sample 2 is analyzed, thereby analyzing and judging sample 2 and performing multi-scale analysis of the material of sample 2.

[0089] It should be noted that, in this embodiment, Figure 1Since no Raman light signal can be excited when X-rays are used to irradiate the sample 2, the X-ray excitation source 1 needs to be replaced, which is very inconvenient. Therefore, in order to simultaneously test the Raman light signal and X-ray absorption, this embodiment also uses an ultraviolet-visible-infrared band excitation source 32 to excite the Raman light signal.

[0090] Specific detection methods, such as Figure 12 The figure shows a specific example of using an off-axis parabolic mirror probe to detect Raman light signals. The configuration of the off-axis parabolic mirror probe and the X-ray acquisition method are the same as those in Example 1. However, this embodiment also includes an ultraviolet-visible-infrared band excitation source 32 and a conversion component.

[0091] The conversion assembly includes a first converging lens 33 , a dichroic mirror 34 , a long-wave pass filter 35 , a second converging lens 36 and a band-pass filter 388 .

[0092] Specifically, see Figure 12 X-rays enter through the through hole 8 on the off-axis parabolic mirror 7 and irradiate point A of the sample 2. Simultaneously, the ultraviolet-visible-infrared band excitation source 32 emits excitation light of a certain wavelength band, which is filtered out by the bandpass filter 388 to remove any stray light other than the excitation light. This light can now be considered parallel light. After passing through the dichroic mirror 34, the short-wavelength light is reflected and the long-wavelength light is transmitted. The excitation light is reflected by the dichroic mirror 34 and directed to the first converging lens 33. The first converging lens 33 converges the excitation light onto the optical fiber, which then enters the off-axis parabolic mirror fiber adapter 29 and is then directed into the probe. At this point, the excitation light is converted to parallel light by the achromatic lens 28 and then converged by the off-axis parabolic mirror 7 to its focal point. Point A of the sample 2 to be measured should be placed at this focal point to generate a Raman light signal. Raman light is light that is scattered elastically and inelastically when it strikes the sample 2 under test. Elastic scattered light has components with the same wavelength as the excitation light, while inelastic scattered light has components with longer and shorter wavelengths than the excitation light, representing the Raman light signal. The Raman light signal is collected by an off-axis parabolic mirror 7 and converted into parallel light. This light is then converged into an optical fiber through an achromatic lens 28. The light collected by the optical fiber passes through a first converging lens 33 and a dichroic mirror 34, passes through a long-wavepass filter 35, and then through a second converging lens 36 before being connected to a first spectrometer 37 for measurement. Simultaneously, X-rays that pass through the sample 2 under test are received by an X-ray detector 6, which measures its X-ray absorption spectrum.

[0093] like Figure 13 The figure shows a specific example of detecting Raman light signals using a plane mirror probe. The plane mirror probe configuration and X-ray acquisition method are consistent with those in Example 1. The remaining structural configuration is consistent with that when using an off-axis parabolic mirror probe, except that the plane mirror fiber adapter 40 of the plane mirror probe is connected to the first converging lens 33.

[0094] Specifically, see Figure 13 , X-rays are injected through the through hole 8 on the plane mirror 38 and irradiate point A of the sample 2. At the same time, the light emitted by the ultraviolet-visible-infrared band excitation source 32 enters the plane mirror probe through the first converging lens 33 in the conversion component. The excitation light is then converted into parallel light by the plane mirror post-achromatic lens 41, and then converged to its focus by the plane mirror pre-achromatic lens 42 and the plane mirror 38. Point A of the sample 2 to be measured should also be placed at the focus. The Raman light generated after excitation is converted into parallel light by the plane mirror pre-achromatic lens 42 and the plane mirror 38, and then converged to the optical fiber by the plane mirror post-achromatic lens 41. The light collected by the optical fiber passes through the first converging lens 33 and the dichroic mirror 34, and is connected to the first spectrometer 37 for measurement after passing through the long-wave pass filter 35 and the second converging lens 36. At the same time, the x-rays passing through the sample 2 to be measured are received by the x-ray detector 6, and its x-ray absorption spectrum can be measured.

[0095] like Figure 14 The figure shows a specific example of detecting Raman light signals using a single-sided objective lens probe. The configuration of the single-sided objective lens probe and the X-ray injection method are consistent with those of the single-sided objective lens probe in Example 1. The configuration of the ultraviolet-visible-infrared band excitation source 32 and the conversion component are consistent with those when using a plane reflector probe in this embodiment.

[0096] Specifically, see Figure 14 , X-rays are directed toward Sample 2 and irradiate point A on Sample 2. The other specific processes are the same as those using a plane mirror probe, except for the different angles of incidence between the collection and excitation light at the probe. The single-sided objective lens probe is tilted, and the excitation light is converged by the single-sided objective lens probe and incident on Sample 2. Simultaneously, the excited Raman light is collected by the probe.

[0097] like Figure 15 The figure shows a specific example of using a dual-lens probe to detect Raman light signals. The dual-lens probe configuration and X-ray injection method are consistent with those in Example 1. However, the conversion assembly here only includes a first converging lens 33, a long-wavelength pass filter 35, a second converging lens 36, and a bandpass filter 388.

[0098] And specifically in this embodiment, see Figure 15, X-rays are directed toward sample 2 and irradiate point A of sample 2. At the same time, the ultraviolet-visible-infrared band excitation source 32 emits a certain band of excitation light, which passes through the bandpass filter 388 to filter out other stray light outside the excitation light. At this time, it can be regarded as parallel light, and reaches the first converging lens 33. The first converging lens 33 converges the excitation light on the optical fiber, and the optical fiber is introduced into one side of the probe. At this time, the excitation light passes through the single-sided objective lens rear lens 15 to convert the excitation light into parallel light, and then passes through the single-sided objective lens front lens 13 to converge to its focus. On the other hand, point A of the sample to be tested 2 should also be placed at the focus. The excited Raman light enters the probe on the other side, is converted into parallel light through the second single-sided objective front lens 17, and then is converged to the optical fiber through the second single-sided objective rear lens 19. The light collected by the optical fiber passes through another first converging lens 33 and is converted into parallel light. After passing through the long-wave pass filter 35 and the second converging lens 36, it is connected to the first spectrometer 37 for measurement. At the same time, the X-rays passing through the sample to be tested 2 are received by the X-ray detector 6, and its X-ray absorption spectrum can be measured.

[0099] The method in this embodiment can also detect and analyze photoluminescence signals. Here, only the excitation light band emitted by the ultraviolet-visible-infrared band excitation source 32 is different. The excitation light used in photoluminescence excitation is often short-wave light. The other structures are consistent with those in Raman light signal detection.

[0100] Example 3

[0101] In this embodiment, an X-ray absorption spectrum combined detection system is used to detect infrared reflection spectrum, and the X-ray absorption of sample 2 and the emission of infrared light signals are analyzed at the same time, so as to analyze and judge sample 2, and thus perform multi-scale analysis of the sample 2 material.

[0102] The principle of infrared reflectance spectroscopy is that an excitation source in the ultraviolet-visible-infrared band emits infrared light of a certain wavelength, and projects this light onto the sample 2 to be measured. The sample molecules vibrate or rotate to absorb light of a specific wavelength, resulting in troughs in the reflectance spectrum. The wavelength range of the infrared reflectance spectrum is consistent with the excitation light. Certain wavelengths of light in this band will be weakened due to sample absorption. The final collected reflectance spectrum is the infrared reflectance spectrum. Since the measurement of infrared reflectance spectrum is essentially to measure the light signal after the original excitation light is reflected, only off-axis parabolic reflector probes, plane reflector probes and double-sided objective lens separation probes can be used. Because they meet the conditions of equal incident angle and reflection angle in geometric optics, they can better collect infrared reflected light.

[0103] Specific detection methods, such as Figure 16The figure shows a specific example of using an off-axis parabolic mirror probe to detect infrared reflection spectrum. The setting of the off-axis parabolic mirror probe and the X-ray intake method are the same as those in Example 1. However, in this embodiment, a second ultraviolet-visible-infrared band excitation source 51 and a fiber combiner 52 are also provided.

[0104] Specifically, see Figure 16 X-rays are directed toward point A of sample 2. Simultaneously, a second ultraviolet-visible-infrared excitation source 51 emits infrared light of a certain wavelength band through a fiber combiner 52. The infrared light then passes through the fiber combiner 52 and the off-axis parabolic mirror fiber adapter 29 before being introduced into the probe. At this point, the infrared light passes through the achromatic lens 28, converting the excitation light into parallel light. The light then passes through the off-axis parabolic mirror 7 and converges to its focal point, where point A of the sample 2 to be tested should be placed. The infrared reflected light, absorbed by the sample, is collected by the off-axis parabolic mirror probe. After passing through the off-axis parabolic mirror 7 and the achromatic lens 28, it enters the fiber combiner 52 through an optical fiber and is transmitted to the fourth spectrometer 50 for detection. Simultaneously, the X-rays that pass through the sample 2 to be tested are received by the X-ray detector 6, and its X-ray absorption spectrum can be measured.

[0105] like Figure 17 The figure shows a specific example of using a plane reflector probe to detect infrared reflection spectrum. The arrangement of the plane reflector probe and the X-ray intake method are the same as those in Example 1.

[0106] Specifically, see Figure 17 , X-rays are directed to point A of the sample 2. At the same time, the second ultraviolet-visible-infrared band excitation source 51 emits infrared light of a certain band through the fiber combiner 52. The infrared light passes through the fiber combiner 52 and the off-axis parabolic mirror fiber adapter 29 and is then introduced into the probe. At this time, the infrared light passes through the plane mirror post-achromatic lens 41 to convert the excitation light into parallel light, and then passes through the plane mirror pre-achromatic lens 42 and the plane mirror 38 to converge the light to its focus, and point A of the sample 2 to be tested should also be placed at the focus. After the infrared light is irradiated on the sample, the probe part performs the collection function again. The infrared light is collected and converted into parallel light by the plane mirror 38 and the plane mirror pre-achromatic lens 42, and then converged to the optical fiber through the plane mirror post-achromatic lens 41, and then enters the optical fiber into the fiber combiner 52 and is transmitted to the fourth spectrometer 50 for detection. At the same time, the x-rays passing through the sample 2 to be tested are received by the X-ray detector 6, and its x-ray absorption spectrum can be measured.

[0107] like Figure 17 The figure shows a specific example of using a double-sided objective lens separation probe to detect infrared reflection spectrum. The configuration of the double-sided objective lens separation probe and the X-ray acquisition method are the same as those in Example 1. However, the fiber combiner 52 is no longer provided.

[0108] And specifically in this embodiment, see Figure 18 , X-rays are directed to point A of the sample 2, and at the same time, the second ultraviolet-visible-infrared band excitation source 51 emits infrared light of a certain band, which is introduced into one side probe by the optical fiber. At this time, the infrared light passes through the single-sided objective lens rear lens 15 to convert the excitation light into parallel light, and then passes through the single-sided objective lens front lens 13 to converge to its focus, and point A of the sample 2 to be tested should also be placed at the focus. The reflected light enters the probe on the other side, passes through the second single-sided objective lens front lens 17 to convert it into parallel light, and then passes through the second single-sided objective lens rear lens 19 to converge to the optical fiber. The light collected by the optical fiber is connected to the fourth spectrometer 50 for detection. At the same time, the x-rays passing through the sample 2 to be tested are received by the X-ray detector 6, and its x-ray absorption spectrum can be measured.

[0109] The terms "installed," "disposed," "equipped with," and "connected" as used herein should be interpreted broadly. For example, they may refer to fixed connections, removable connections, or integral structures; mechanical connections or electrical connections; direct connections, indirect connections through an intermediary, or internal communication between two devices, elements, or components. Those skilled in the art will understand the specific meanings of these terms in this application based on the specific circumstances.

[0110] The above is a schematic description of the present invention and its embodiments, which is not restrictive. The drawings show only one embodiment of the present invention, and the actual structure is not limited thereto. Therefore, if a person skilled in the art is inspired by this and, without departing from the purpose of the present invention, designs a structure and embodiment similar to this technical solution without inventiveness, they shall fall within the scope of protection of the present invention.

Claims

1. A combined detection system for X-ray absorption spectroscopy, characterized by: It includes an X-ray excitation source (1), a fiber-coupled optical path module and an X-ray detector (6); The X-ray excitation source (1) is arranged directly above the sample (2) to be detected and is capable of emitting X-rays vertically to illuminate point A of the sample (2); the X-ray detector (6) is located directly below point A of the sample (2) and is used to detect X-ray signals after passing through the sample (2); At the same time, the A of the sample (2) can be excited to emit a light signal to be measured, and the light signal to be measured is emitted in different directions close to one side of the sample (2); The fiber-coupled optical path module is connected to the spectrometer and is located at different positions above the sample (2) for collecting the optical signal to be measured and transmitting the optical signal to be measured to the spectrometer for detection; when the fiber-coupled optical path module is located directly below the X-ray excitation source (1), a through hole (8) is provided on the fiber-coupled optical path module for the X-ray to pass through.

2. The combined detection system for X-ray absorption spectroscopy according to claim 1, characterized in that: The light signal to be measured that is excited on the sample (2) is generated when the X-rays emitted by the X-ray excitation source (1) irradiate the sample (2).

3. The combined detection system of X-ray absorption spectroscopy according to claim 1, characterized in that: It also includes an ultraviolet-visible-infrared band excitation source, which is connected to the fiber-coupled optical path module; The light signal to be measured excited on the sample (2) is excited by the light signal emitted by the ultraviolet-visible-infrared band excitation source and focused and irradiated onto the sample (2) through the optical fiber coupling optical path module.

4. The combined detection system for X-ray absorption spectroscopy according to claim 2 or 3, characterized in that: The fiber-coupled optical path module is an off-axis parabolic mirror probe, which comprises an off-axis parabolic mirror (7) arranged at one end of the off-axis parabolic mirror probe and an achromatic lens (28) located inside the off-axis parabolic mirror probe; the off-axis parabolic mirror (7) is located directly below the X-ray excitation source (1), and the through hole (8) is provided on the off-axis parabolic mirror (7); the off-axis parabolic mirror (7) faces the side of the sample (2), and an opening is provided on the off-axis parabolic mirror probe.

5. The combined detection system of X-ray absorption spectroscopy according to claim 2 or 3, characterized in that: The fiber-coupled optical path module is a plane mirror probe, which includes a plane mirror (38) arranged at one end of the plane mirror probe, a plane mirror rear achromatic lens (41) and a plane mirror front achromatic lens (42) located inside the plane mirror probe, wherein the plane mirror front achromatic lens (42) is arranged at one end close to the plane mirror (38); the plane mirror (38) is located directly below the X-ray excitation source (1), and the through hole (8) is provided on the plane mirror (38); the plane mirror (38) faces the side of the sample (2), and an opening is provided on the plane mirror probe.

6. The combined detection system of X-ray absorption spectroscopy according to claim 2 or 3, characterized in that: The fiber-coupled optical path module is an objective lens probe, and the objective lens probe is single-sided or double-sided; The objective lens probe is tilted and located obliquely to the side of the X-ray irradiation path. The objective lens probe includes a front lens and a rear lens respectively arranged near its two ends; the objective lens probe has an opening at one end facing the sample (2).

7. The combined detection system of X-ray absorption spectroscopy according to claim 1, characterized in that: The through hole (8) has a diameter of 1-10 mm.

8. The combined detection system of X-ray absorption spectroscopy according to claim 2 or 3, characterized in that: The optical signal to be measured includes one of a scintillator fluorescence signal, a Raman light signal, a photoluminescence signal and an infrared reflectance spectrum light signal.

9. A detection method using a combined detection system of X-ray absorption spectroscopy, characterized in that: The X-ray excitation source (1) is arranged directly above the sample (2) to be detected and is capable of emitting X-rays vertically toward position A of the sample (2); The X-ray detector (6) is positioned directly below the sample (2) to detect X-ray signals after passing through the sample (2); At the same time, the sample (2) A is excited to emit a light signal to be measured, and the light signal to be measured is emitted in different directions close to a side of the sample (2); The fiber-coupled optical path module is connected to a spectrometer and is arranged at different positions above the sample (2) to collect the optical signal to be measured, and the optical signal to be measured is transmitted to the spectrometer for detection; When the fiber-coupled optical path module is located directly below the X-ray excitation source (1), a through hole (8) is provided on the fiber-coupled optical path module for X-rays to pass through.

10. An application of a combined detection system for X-ray absorption spectroscopy, characterized in that: A combined detection system comprising the X-ray absorption spectrum according to any one of claims 1 to 8, which simultaneously detects the X-rays transmitted at point A of the sample (2) and the light signal to be measured excited at that point, for multi-scale analysis of the sample (2) material to be detected.

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