High-resolution cross-scale X-ray fluorescence spectrum high-throughput characterization device and method

Abstract

The invention discloses a high-resolution cross-scale X-ray fluorescence spectrum high-flux characterization device and method. The device comprises a mu-XRF light source (an X-ray tube and a capillary X-ray lens), a plurality of SDD detectors, a sample box and a two-dimensional mobile platform which are sequentially arranged from top to bottom, x-rays emitted by the X-ray tube are restrained by the capillary X-ray lens into focuses with the diameter of 5 microns to vertically irradiate a sample, the whole mu-XRF light source adopts a fixed support structure capable of moving up and down, and cross-scale adjustment of beam spots in the range of 5 microns to 1 mm on the surface of the sample is realized; the plurality of SDD detectors are arranged at the periphery of the capillary X-ray lens in a surrounding manner at a set inclination angle, and synchronously collect spectral information of X-ray fluorescence; a sample box is placed on the two-dimensional moving platform, and the sample box can contain plane samples of different sizes. According to the invention, a high-throughput XRF device structure is independently developed, and rapid and accurate cross-scale X-ray fluorescence spectrum high-throughput quantitative characterization can be realized.

Description

Technical Field

[0001] The present invention relates to the technical field of microbeam X-ray fluorescence spectroscopy analysis, and in particular to a high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device and method. Background Art

[0002] Microbeam X-ray fluorescence spectrometry (μ-XRF) is an important method for material composition analysis. Its high-resolution, nondestructive testing, and simultaneous, high-speed characterization of multi-element surface distributions offer significant application value in the field of materials analysis. μ-XRF can be used to determine the thickness and composition of various materials. For example, the performance of semiconductor devices depends on precisely controlled doping levels and impurity content. μ-XRF can be used to rapidly detect the elemental composition of semiconductor materials such as silicon wafers. The optical properties of electro-optical materials, such as refractive index and absorption coefficient, are closely related to their chemical composition. μ-XRF can be used to analyze the composition of these materials to ensure their performance. The efficiency of solar cells is affected by their material composition and thickness. μ-XRF can be used to analyze the elemental distribution in thin-film solar cells, including absorber and buffer layers. In the electronics industry, μ-XRF can be used to analyze the chemical composition of circuit boards, solder, and packaging materials to ensure the quality and reliability of electronic equipment. In the aerospace, automotive, and pharmaceutical industries, μ-XRF can be used to analyze alloy composition, coating thickness, and surface treatments. Improvements in electronics and optimization of data processing algorithms have made μ-XRF analysis faster. After the sample is placed in the instrument, the analysis results can be obtained in a very short time. It can directly analyze samples in various forms such as solids, powders, and liquids, reducing the complexity and time of sample preparation, making it suitable for real-time monitoring and quality control in the production process.

[0003] Currently, Germany's Bruker μ-XRF instruments dominate the global market, followed by products from the US company IXRF. There are no commercially available domestic instruments of this type. Bruker's μ-XRF spectrometers are technologically mature and offer high-performance analytical capabilities. The M4 TORNADO series is designed for highly sensitive and non-destructive elemental analysis, suitable for examining heterogeneous and irregularly shaped samples. However, Bruker's instruments still have some shortcomings: the resolution of the 20μm beam spot is insufficient for high-precision analysis, and the beam spot is obliquely incident on the sample surface, causing beam spot deformation and reduced resolution. The beam spot has only two setting parameters: 20μm and 170μm, with a limited range, which limits its adaptability to cross-scale characterization and material applicability. When magnifying the beam spot, the sample platform is lowered, and the detector moves away from the sample surface, resulting in a significant decrease in signal intensity and reduced detection efficiency. Furthermore, the system can only accommodate up to two detectors, which limits analysis speed. IXRF, a US-based company specializing in XRF technology, has achieved significant research and development in the field of μ-XRF spectrometers. Its latest flagship product, the ATLAS X, is a universal microbeam XRF spectrometer for measuring and imaging / mapping elements from sodium (Na) to uranium (U). While the ATLAS X has broad applications across multiple fields, it also has some drawbacks. Like Bruker, the ATLAS X uses a lowered sample platform to adjust the beam spot size to suit different samples or analytical requirements. This increases the distance between the detector and the sample surface, significantly reducing signal intensity. This design compromises analytical sensitivity and accuracy, particularly in applications requiring high resolution and sensitivity. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device. The high-throughput XRF device structure is independently developed. The beam spot on the sample surface can be adjusted across the scale of 5μm-1mm. X-rays irradiate the sample surface vertically to obtain high-resolution component distribution information, realize XRF-based microstructure distribution characterization, integrate multiple SDD detectors to improve acquisition efficiency, and realize fast and accurate high-throughput quantitative characterization.

[0005] To achieve the above object, the present invention provides the following solutions: A high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device, comprising: a μ-XRF light source, multiple SDD detectors, a sample box and a two-dimensional mobile platform arranged in sequence from top to bottom; The μ-XRF light source includes an X-ray tube and a capillary X-ray lens; The capillary X-ray lens is connected to the X-ray tube to constrain the X-rays emitted by the X-ray tube to a focus with a diameter of 5 μm to irradiate the sample surface vertically; The μ-XRF light source adopts a fixed bracket structure that can be moved up and down, which enables cross-scale adjustment of the beam spot on the sample surface within the range of 5μm-1mm; Multiple SDD detectors are arranged around the periphery of the capillary X-ray lens at a set inclination angle for synchronously collecting spectral information of X-ray fluorescence; the SDD detectors are connected to a processor, and the processor processes the spectral information of X-ray fluorescence to achieve high-throughput characterization of X-ray fluorescence spectra; The two-dimensional moving platform is located directly below the capillary X-ray lens, a sample box is placed on the two-dimensional moving platform, and the two-dimensional moving platform is used to drive the sample box to move and scan in a planar direction; An elastic support is provided in the sample box for holding planar samples of different sizes and lifting the planar samples to make close contact with the inner surface of the box cover.

[0006] Furthermore, at least four SDD detectors are provided.

[0007] Furthermore, the distance between the SDD detector and the sample surface is 15 mm.

[0008] Furthermore, the set inclination angle is 30°~60°.

[0009] Furthermore, the device is arranged in a vacuum chamber.

[0010] Furthermore, the elastic support is a spring, one end of the spring is connected to the bottom of the sample box, and the other end abuts against the plane sample.

[0011] The present invention also provides a high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization method, which is applied to the above-mentioned high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device, comprising the following steps: Move the μ-XRF light source and place the X-rays emitted by the capillary X-ray lens on the sample surface so that the X-ray beam spot reaches the desired size; Adjust the two-dimensional moving platform to move the sample box in the plane direction to scan the sample surface; Multiple SDD detectors synchronously collect spectral information of X-ray fluorescence and transmit it to the processor; The processor processes the spectral information of X-ray fluorescence to achieve high-throughput characterization of X-ray fluorescence spectra.

[0012] Furthermore, the X-ray fluorescence spectroscopy high-throughput characterization includes high-resolution component distribution analysis, high-throughput component statistical distribution characterization, and rapid quantitative analysis of the macroscopic average component of a large beam spot.

[0013] According to a specific embodiment provided by the present invention, the high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device provided by the present invention discloses the following technical effects: (1) The μ-XRF light source beam spot can be continuously changed from microscopic 5μm high resolution to macroscopic 1 mm large size. The structure design of the X-ray tube fixed bracket that can be moved up and down is adopted to achieve cross-scale adjustment of the beam spot in the range of 5μm-1 mm on the sample surface. (2) The design of X-ray vertical irradiation of the sample surface avoids the uniaxial elongation of the beam spot caused by oblique irradiation of the analysis surface, and the beam spot position does not shift when the X-ray source moves up and down and defocuses, which can more accurately control the analysis position; (3) Design of a synchronous acquisition structure of multiple SDD detectors, integrating multiple SDD detectors to synchronously acquire spectral signals to improve acquisition efficiency, optimizing the distance between the SDD detector and the sample surface to maximize the intensity of each detector, and achieving the best cost-effectiveness of the instrument, maximizing the intensity signal, and maximizing the acquisition efficiency; (4) The specially designed sample box can ensure the flat samples of different sizes. There is a high-strength elastic bracket (such as a spring) in the sample box to lift the sample and make close contact with the inner surface of the box cover. The height of the sample box is matched with the sample stage of the XRF device so that the sample surface is just at the 5μm focus point of the XRF. The distance and angle between the SDD detector and the sample surface are also at the point where the received light intensity is the largest. This design can ensure that the surfaces of samples of various sizes and thicknesses are at the same height, with the smallest light spot and the position with the largest detector intensity. By moving the μ-XRF light source up and down, the focus can be defocused above the sample surface to change the beam spot size on the sample surface, but it will not affect the light intensity signal received by the SDD. (5) It is also possible to conduct research on the structural design of a vacuum-type large sample chamber instrument. The device is set in a vacuum chamber, and comprehensive research is carried out on the optimization of the size and vacuum degree of the vacuum chamber, the structure and layout design of the mobile platform, the sealing structure design of the X-ray tube and detector, and the structural design of the protection against external X-ray radiation, so as to realize the detection of low atomic number elements such as Na, Mg, and Al for large-size samples under vacuum. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0015] Figure 1Schematic diagram of the structure of the high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device of the present invention; Figure 2 This is a schematic structural diagram of a sample box according to an embodiment of the present invention; Figure 3 Schematic diagram of high-resolution composition distribution when the XRF beam spot diameter is as small as 5 μm in an embodiment of the present invention. (a) is a schematic diagram of the working principle of the high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device, (b) is a diagram of two pure Pt circular spots separated by 10 μm, and (c) is a two-dimensional diagram of the Pt composition distribution. Figure 4 Schematic diagram of the composition distribution of different elements in a nickel-based superalloy when the XRF beam spot diameter is 20 μm according to an embodiment of the present invention; (a) is a schematic diagram of the working principle of a high-throughput characterization device for mesoscopic X-ray fluorescence spectroscopy, (b) shows the composition distribution of an as-cast superalloy, and (c) shows the composition distribution of a heat-treated superalloy; Figure 5 Schematic diagram of the composition distribution of different elements in a multi-component array sample using mesoscopic resolution when the XRF beam spot diameter is 20 μm in an embodiment of the present invention; (a) is a multi-component array sample, and (b) is a schematic diagram of high-throughput composition distribution characterization of the multi-component array sample; Figure 6 Figure 1 is a schematic diagram of the rapid quantitative analysis of the macroscopic average composition of a large XRF spot with a diameter of 1 mm according to an embodiment of the present invention. (a) is a schematic diagram of the working principle of the high-throughput characterization device for macroscale X-ray fluorescence spectroscopy, (b) represents a multi-component array sample, and (c) represents the quantitative analysis test of a small-size sample with a width of 4 mm using a 1 mm spot.

[0016] Explanation of the accompanying symbols: 1. X-ray tube; 2. Capillary X-ray lens; 3. SDD detector; 4. Sample box; 5. Two-dimensional moving platform; 6. X-ray tube fixing bracket; 7. Vacuum chamber; 8. X-ray focus; 9. X-ray beam spot. DETAILED DESCRIPTION

[0017] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0018] The purpose of the present invention is to provide a high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device, whose minimum beam spot size can reach 5μm, and the beam spot can be adjusted across the scale from 5μm to 1 mm. The beam spot irradiates the sample surface vertically to obtain high-resolution composition distribution information and establish an XRF-based microstructure distribution characterization method; it integrates ≥4 SDD detectors to improve acquisition efficiency and can detect low atomic number elements such as Na, Mg, and Al under vacuum.

[0019] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0020] like Figure 1 As shown, the high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device provided by the present invention includes: a μ-XRF light source, an SDD detector 3, a sample box 4 and a two-dimensional mobile platform 5 arranged in sequence from top to bottom; The μ-XRF light source includes an X-ray tube 1 and a capillary X-ray lens 2; The μ-XRF light source adopts a structure of a fixed bracket that can be moved up and down, so that the beam spot on the sample surface can be adjusted across the scale within the range of 5μm-1mm; the μ-XRF light source is fixed to the upper part of the vacuum chamber 7 by an X-ray tube fixed bracket 6, and the μ-XRF light source is moved up and down by an electric translation stage, with a vertical travel range of ≤50mm; The capillary X-ray lens 2 is connected to the X-ray tube 1 to irradiate the X-ray vertically onto the sample surface; At least four SDD detectors 3 are arranged around the periphery of the capillary X-ray lens at a set inclination angle of 30° to 60°, for synchronously collecting spectral information of X-ray fluorescence; the distance between the SDD detector and the sample surface is 15 mm; for example, the SDD detector array includes 4-8 independent probes, and the central axis of each probe is inclined at 45° to the vertical direction.

[0021] The SDD detector 3 is connected to a processor, which processes the spectral information of X-ray fluorescence to achieve high-throughput characterization of X-ray fluorescence spectra. For example, the processor has a built-in FPGA parallel processing module to achieve synchronous acquisition of multi-detector signals, adopts the Monte Carlo algorithm for element quantitative analysis, and supports high-speed processing of 1,000 spectral data per second.

[0022] The two-dimensional moving platform 5 is located directly below the capillary X-ray lens 2, and a sample box 4 is placed on the two-dimensional moving platform 5. The two-dimensional moving platform 5 is used to drive the sample box 4 to move in the planar direction; for example, the two-dimensional moving platform 5 is driven by a stepper motor, with an X / Y axis stroke of ≥200mm, a repeatability accuracy of ≤0.5μm, and an adjustable movement speed range of 0.01-50mm / s. Existing commercial instruments in this field directly place samples of different heights on the sample stage, and then adjust the upper and lower heights of the sample stage to place the minimum focused beam spot of the X-ray source on the sample surface. Each time the sample is changed, adjustments are required, which is very cumbersome. The present invention determines the minimum focused spot of the X-ray source on the sample surface by superimposing a fixed height on the two-dimensional moving sample stage and the sample box, without the need to find a focusing point, which is more convenient.

[0023] like Figure 2 As shown, the sample box 4 can be cylindrical, and an elastic support is provided inside the sample box 4 to hold planar samples of different sizes, lifting the planar samples and bringing them into close contact with the inner surface of the box cover. Specifically, the elastic support is a spring, one end of which is connected to the bottom of the sample box, and the other end abuts against the planar sample.

[0024] In addition, the device is arranged in a vacuum chamber and can detect low atomic number elements such as Na, Mg, and Al for large-sized samples under vacuum.

[0025] On the other hand, the present invention also provides a high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization method, which is applied to the above-mentioned high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device, comprising the following steps: Move the μ-XRF light source and defocus the X-ray focus emitted by the capillary X-ray lens above the sample surface so that the X-ray beam spot on the sample surface reaches the desired size; Adjust the two-dimensional moving platform to move the sample box in the plane direction to scan the sample surface; Multiple SDD detectors synchronously collect spectral information of X-ray fluorescence and transmit it to the processor; The processor processes the spectral information of X-ray fluorescence to achieve high-throughput characterization of X-ray fluorescence spectra.

[0026] Example 1: High-resolution composition distribution analysis like Figure 3 As shown in (a), the μ-XRF light source is moved and the focus of the X-ray emitted by the capillary X-ray lens 2 is placed on the sample surface. At this time, the XRF beam spot diameter is d The highest resolution of the analysis is about 5 μm. Figure 3 (b) shows two pure Pt circular spots with a spacing of 10 μm, obtained after XRF scanning. Figure 3The two-dimensional distribution diagram of Pt composition in (c) shows that intervals of 10 μm can be clearly distinguished, indicating that the resolution of this analysis method is better than 10 μm.

[0027] Example 2: High-throughput component statistical distribution characterization like Figure 4 As shown in (a), the μ-XRF light source is moved upward, and the focus of the X-rays emitted by the capillary X-ray lens 2 is placed 4 mm above the sample surface. At this time, the XRF beam spot diameter is about 20 μm, which is in a relatively high-resolution state, allowing non-destructive component statistical distribution analysis of the material surface.

[0028] Figure 4 Figures (b) and (c) show the compositional distribution of different elements in nickel-based superalloys. This allows identification of the segregation of different elements between dendrites and along dendrite stems, thereby assessing the material's microscopic uniformity and guiding the segregation behavior of various elements as the metal cools from liquid to solid. Furthermore, it allows for the statistical analysis of dendrite spacing parameters based on specific elements (such as Re and Co), potentially replacing traditional metallographic analysis methods for observing dendrite spacing.

[0029] Figure 5 (a) is an array sample, and (b) is a schematic diagram of the characterization of 106 nickel-based high-temperature alloy array samples with different compositions rapidly synthesized by hot isostatic pressing. Co, Ta, Nb and Ni elements are evenly distributed in each cell, and the distribution of Fe and Al elements respectively calibrates the position of the inner wall of the stainless steel honeycomb structure.

[0030] Example 3: Rapid quantitative analysis of the macroscopic average composition of a large beam spot like Figure 6 As shown in (a), the μ-XRF light source is moved upwards and the X-ray focus emitted by the capillary X-ray lens is placed 40 mm above the sample surface. At this time, the XRF beam spot diameter is It is about 1mm, in a macroscopic large beam spot state, and is the most efficient and accurate in quantifying the average composition of the material.

[0031] Figure 6 Middle (b) shows the quantitative characterization of the composition of each component in a multi-component array sample. A 1mm beam spot is used to perform quantitative analysis and testing on a small-size sample with a width w of 4mm. The single-point test time is 25s. The entire sample contains 106 small-size samples, and the test takes a total of 50 minutes, achieving fast and accurate high-throughput quantitative characterization.

[0032] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only intended to help understand the method and core concept of the present invention. At the same time, those skilled in the art will find that the specific implementation methods and application scopes may vary based on the concept of the present invention. In summary, the contents of this specification should not be construed as limiting the present invention.

Claims

1. A high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device, characterized in that: include: The μ-XRF light source, multiple SDD detectors, sample box and two-dimensional mobile platform are arranged in sequence from top to bottom; The μ-XRF light source includes an X-ray tube and a capillary X-ray lens; The capillary X-ray lens is connected to the X-ray tube to constrain the X-rays emitted by the X-ray tube to a focus with a diameter of 5 μm to vertically irradiate the sample surface; The μ-XRF light source adopts a fixed bracket structure that can be moved up and down, which enables cross-scale adjustment of the beam spot on the sample surface within the range of 5μm-1mm; Multiple SDD detectors are arranged around the periphery of the capillary X-ray lens at a set inclination angle of 30° to 60°, and are used to synchronously collect spectral information of X-ray fluorescence; the SDD detectors are connected to a processor, and the processor processes the spectral information of X-ray fluorescence to achieve high-throughput characterization of X-ray fluorescence spectra; The two-dimensional moving platform is located directly below the capillary X-ray lens, a sample box is placed on the two-dimensional moving platform, and the two-dimensional moving platform is used to drive the sample box to move in a two-dimensional plane; An elastic support is provided in the sample box for holding planar samples of different sizes and lifting the planar samples to make close contact with the inner surface of the box cover.

2. The high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device according to claim 1, characterized in that: At least four SDD detectors are provided.

3. The high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device according to claim 1, characterized in that: The distance between the SDD detector and the sample surface is 15 mm.

4. The high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device according to claim 1, characterized in that: The set inclination angle is 30°~60°.

5. The high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device according to claim 1, characterized in that: The device is arranged in a vacuum chamber.

6. The high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device according to claim 1, characterized in that: The elastic support is a spring, one end of which is connected to the bottom of the sample box, and the other end of which abuts against the plane sample.

7. A high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization method, applied to the high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization device according to any one of claims 1 to 6, characterized in that: The steps include: Move the μ-XRF light source up and down, and place the X-ray focus emitted by the capillary X-ray lens vertically on the sample surface or above the sample in a defocused state, so that the X-ray fluorescence beam spot on the sample surface reaches the required size; Adjust the two-dimensional moving platform to move the sample box in the plane direction to scan the sample surface; Multiple SDD detectors synchronously collect spectral information of X-ray fluorescence and transmit it to the processor; The processor processes the spectral information of X-ray fluorescence to achieve high-throughput characterization of X-ray fluorescence spectra.

8. The high-resolution cross-scale X-ray fluorescence spectroscopy high-throughput characterization method according to claim 7, wherein the X-ray fluorescence spectroscopy high-throughput characterization includes high-resolution component distribution analysis, high-throughput component statistical distribution characterization, and rapid quantitative analysis of large beam spot macroscopic average components.

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