A multiphase Ta based on EDXs x C 1-x Fully quantitative analysis method

Abstract

The present invention provides a multi-phase Ta based on EDXs x C 1‑x A fully quantitative analysis method belongs to the technical field of fully quantitative analysis of metal compounds and comprises: preparing a TaC compound sample; collecting an actual measurement spectrum of the TaC compound sample; analyzing the actual measurement spectrum to obtain a real sample of TaL / CK and / or TaM / CK values; changing the position at which an X-ray spectrometer probe penetrates the TaC compound sample so that the thickness of the TaC compound sample varies between 100 nm and 1000 nm, repeating steps S02 and S03, and producing a first relationship curve diagram between TaL / CK and TaC compound sample thickness, and / or between TaM / CK and TaC compound sample thickness; determining, based on the first relationship curve diagram, a critical thickness D1 of the TaC compound sample when the TaL / CK and / or TaM / CK values ​​tend to be stable; establishing a simulated spectrum library, selecting a first real sample with a thickness not less than the critical thickness D1, and comparing a first actual measurement spectrum corresponding to the first real sample with the simulated spectrum library, so that the corresponding Ta and C contents are the real Ta and C contents in the TaC compound sample.

Description

Technical Field

[0001] The present invention relates to the technical field of full quantitative analysis of metal compounds, in particular to a multi-phase Ta-based x C 1-x Fully quantitative analysis method. Background Art

[0002] Experimentally, during the manufacturing process of TaC, the synthesized TaC solid solution may contain a mixed phase of TaC, TaC2, and Ta4C3, which can easily affect the mechanical properties of the sample. Therefore, the full quantitative determination of TaC and its related crystalline phases will help materials scientists synthesize mixed TaC phases with superior mechanical properties.

[0003] Energy Dispersive X-ray Spectrometers (EDXs), short for energy dispersive X-ray spectrometers, analyze the wavelength and intensity of elemental X-rays emitted by a sample. The elements present in the sample are determined based on the differences in the wavelengths of the characteristic X-rays. By comparing the intensities of the spectral lines of different elements, the elemental content in the sample can be determined. EDXs are often used in conjunction with electron microscopy to perform micro-area compositional analysis of samples.

[0004] The patent with publication number CN108051466A discloses a non-destructive quantitative detection method for fertilizer components based on X-ray fluorescence spectroscopy analysis, including: S1. Collection and pretreatment of fertilizer samples; S2. Determination of the components of the fertilizer samples using standard chemical methods, and collection of standard spectra of the fertilizer samples by X-ray spectrometer; S3. Selection of fertilizer samples in the calibration set; S4. Background subtraction of the X-ray fluorescence spectrum; S5. Curve fitting of the X-ray fluorescence spectrum; S6. Determination of the nonlinear mapping relationship between the content of each element in the fertilizer samples in the calibration set and the characteristic peak intensity of their X-ray fluorescence spectra based on the nonlinear multivariate correction method in chemometrics, and establishment of a nonlinear dynamic correction model; S7. Detection of the content of each component in the unknown fertilizer sample: first scan the X-ray fluorescence spectrum of the unknown fertilizer sample, bring it into the nonlinear dynamic correction model of step S6, and calculate the content of each component in the unknown fertilizer sample.

[0005] When using EDXs to detect the composition of TaC, after the characteristic X-ray photons enter the sample, they will experience absorption, scattering, transmission and other losses in the sample, which will affect the accuracy of the measured sample composition results and is not conducive to more accurate calculation and analysis of the material composition. Summary of the Invention

[0006] In view of the above problems in the prior art, the present invention provides a multi-phase Ta based on EDXs. x C 1-x Fully quantitative analysis method.

[0007] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is as follows:

[0008] Providing a multiphase Ta based on EDXs x C 1-x The fully quantitative analysis method includes the following steps:

[0009] S01, preparing TaC compound samples;

[0010] S02. collecting an actual measurement spectrum of the TaC compound sample by an X-ray spectrometer;

[0011] S03. Analyze the actual measured spectrum to obtain a true sample of TaL / CK and / or TaM / CK values;

[0012] S04. Changing the position at which the probe of the X-ray spectrometer is inserted into the TaC compound sample so that the thickness of the TaC compound sample under the probe varies between 100 nm and 1000 nm, repeating steps S02 and S03, and generating a first relationship curve between TaL / CK and TaC compound sample thickness, and / or TaM / CK and TaC compound sample thickness;

[0013] S05. Determine, based on the first relationship curve, a critical thickness D1 of the TaC compound sample when the value of TaL / CK and / or TaM / CK tends to be stable;

[0014] S06. Establish a simulated spectrum library of simulated characteristic spectra for different Ta and C contents in a TaC compound obtained through computer simulation, select a first real sample of the TaC compound sample under the probe whose thickness is not less than a critical thickness D1, compare a first actually measured spectrum corresponding to the first real sample with the simulated spectrum library to obtain a best-matched target characteristic spectrum, and determine that the Ta and C contents corresponding to the target characteristic spectrum are the actual Ta and C contents in the TaC compound sample.

[0015] Furthermore, in step S03, the actual measured spectrum is analyzed, including:

[0016] Based on the actual measured spectra, the background maps of TaL, TaM and CK were drawn using casino software. After Gaussian fitting of the background maps of TaL, TaM and CK, the values ​​of TaL / CK and TaM / CK were determined based on the peak intensities of the X-ray spectra of TaL, TaM and CK in the background maps of TaL, TaM and CK.

[0017] Furthermore, the TaC compound sample includes a substrate and a target body, the substrate is made of epoxy resin, the target body includes a TaC compound, the target body is fixed on the top wall of the substrate, and the surface of the target body is flush with the surface of the substrate.

[0018] Furthermore, the method further includes the following steps:

[0019] S07. Based on the measured actual Ta and C contents, the thickness of the substrate in the TaC compound sample is maintained at a constant value D2, and the thickness of the target under the probe is varied between 100 nm and 1000 nm. Steps S02 and S03 are repeated, and a second relationship graph of TaL / CK and target thickness, and / or TaM / CK and target thickness is generated.

[0020] S08. A third relationship curve diagram of TaL / CK and thickness of the simulated TaC compound, and / or TaM / CK and thickness of the simulated TaC compound, when the thickness of the simulated TaC compound having actual Ta and C contents varies between 100 nm and 1000 nm by computer simulation;

[0021] S09. Compare the second relationship curve diagram and the third relationship curve diagram, and select the target body thickness D3 when the curves in the two relationship curve diagrams converge. When:

[0022] -10nm≤D1-(D2+D3)≤10nm

[0023] It was confirmed that the substrate had no effect on the quantification of Ta and C.

[0024] Furthermore, the target body is hemispherical, with the spherical surface of the target body facing the substrate, and the diameter of the target body is 4*e 6 nm;

[0025] In step S04, the probe of the X-ray spectrometer moves horizontally and linearly from the interface between the target and the substrate toward the center of the target, and a first relationship curve is generated. At the same time, a fourth relationship curve between the thickness of the TaC compound sample and the horizontal movement distance of the probe is generated.

[0026] According to the critical thickness D1, the fourth relationship curve is searched to obtain the horizontal moving distance D4 of the probe, and the horizontal moving distance D4 of the probe is determined to be 4*e with the center of the target body as the center. 6 In the region of nm-2D4 as the diameter, the measured TaL / CK and / or TaM / CK values ​​tend to be stable.

[0027] Furthermore, the method further includes the following steps:

[0028] S10. Calculate the calculated Ta and C contents based on the X-ray spectrum peak intensities of TaL, TaM, and CK of the first real sample in step S06 using the Cliff-Lorimer factor calculation formula, and compare the true Ta and C contents with the calculated Ta and C contents. When it is determined that the difference between the true Ta and C contents and the calculated Ta and C contents is less than 8%, it is determined that the measured true Ta and C contents are accurate.

[0029] The beneficial effects of the present invention are as follows: 1. The actual spectrum of the TaC compound is collected by an X-ray spectrometer, and based on the TaL / CK and / or TaM / CK values, the influence of the sample's own factors on the measurement results is eliminated in multiple measurements to obtain a more stable and accurate true Ta and C content of the compound.

[0030] 2. By excluding the influence of sample factors and comparing the spectra of different phase contents of standard compounds, the true content of each phase in the stable compound can be obtained, which can simplify the calculation process of the true content of each phase of the compound and improve the error tolerance rate in the calculation process.

[0031] 3. The influence of factors such as sample thickness, epoxy resin substrate, and the position of X-ray penetration of the spectrometer probe into the sample on the quantitative measurement of compounds is eliminated, and the full quantitative measurement of the content of each phase of the compound is achieved. The measurement results are accurate and help to synthesize compounds with better performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a flowchart of the steps of the analysis method of an embodiment of the present application;

[0033] Figure 2 Schematic diagram of the overall structure of the TaC compound sample of the embodiment of the present application;

[0034] Figure 3 A first relationship curve diagram of TaL / CK and TaC compound sample thickness (left) and TaM / CK and TaC compound sample thickness (right) according to an embodiment of the present application;

[0035] Figure 4 Schematic diagram of the cross-sectional structure of the TaC compound sample according to the embodiment of the present application;

[0036] Figure 5 Schematic diagrams showing a comparison between the second relationship curve and the third relationship curve when measuring TaL / CK (left) and a comparison between the second relationship curve and the third relationship curve when measuring TaL / CK (right) according to an embodiment of the present application.

[0037] Among them, 1, substrate; 2, target body; 101, probe. DETAILED DESCRIPTION

[0038] In order to better understand the above technical solution, the above technical solution will be described in detail below with reference to the accompanying drawings and specific implementation methods.

[0039] The embodiment of the present invention provides a multi-phase Ta based on EDXs. x C 1-x Full quantitative analysis method, refer to Figure 1 、 2, the analysis method may include the following steps:

[0040] S01. Prepare a TaC compound sample. The TaC compound sample primarily comprises a substrate 1 and a target 2. Target 2 is primarily composed of a TaC compound. In this embodiment, substrate 1 may be made of epoxy resin. The target is embedded in the top wall of substrate 1 so that the surface of target 2 is flush with the surface of substrate 1.

[0041] S02. Collecting actual measured spectra of the TaC compound sample using an X-ray spectrometer. The X-ray spectrometer used in this application is a JEOL7800F scanning electron microscope equipped with an Oxford Instruments XMAX SDD EDXs system, wherein the X-ray take-off angle is set to 29° and the detector solid angle is nominally 0.04487.

[0042] S03. Analyze the actual measured spectrum. Based on the actual measured spectrum, create background maps of TaL, TaM, and CK using casino software. After Gaussian fitting of the background maps of TaL, TaM, and CK, determine the actual sample values ​​of TaL / CK and / or TaM / CK based on the peak intensities of the X-ray spectra of TaL, TaM, and CK in the background maps of TaL, TaM, and CK. Specifically, based on the actual measured spectrum of the TaC compound sample measured by the spectrometer, use casino software to obtain background maps of TaL, TaM, and CK, respectively. Then, fit the TaM peak CK with a Gaussian function, and fit the TaM peak with an MLLS Gaussian function. After fitting, the complete peak intensities of the X-rays of TaL, TaM, and CK can be obtained, thereby determining the values ​​of TaL / CK and TaM / CK.

[0043] S04, reference Figure 3 The position of X-ray probe 101 inserted into the TaC compound sample is changed, so that the thickness of the TaC compound sample under probe 101 varies between 100 nm and 1000 nm, with each thickness change being 50 nm. Steps S02 and S03 are repeated, and a first relationship graph is generated between TaL / CK and TaC compound sample thickness, and / or TaM / CK and TaC compound sample thickness.

[0044] S05. Determine, based on the first relationship curve, the critical thickness D1 of the TaC compound sample when the value of TaL / CK and / or TaM / CK tends to be stable.

[0045] S06. Establish a simulated spectrum library of simulated characteristic spectra for different Ta and C contents in a TaC compound obtained through computer simulation. Select a first real sample of the TaC compound sample under the probe 101, wherein the thickness is not less than the critical thickness D1. Compare a first actually measured spectrum corresponding to the first real sample with the simulated spectrum library to obtain a best-matched target characteristic spectrum. Determine that the Ta and C contents corresponding to the target characteristic spectrum are the actual Ta and C contents in the TaC compound sample.

[0046] By taking any sample thickness when the actually measured TaL / CK and / or TaM / CK values ​​are in a steady state as the first real sample, software is used to automatically simulate and establish a simulated spectrum library composed of simulated characteristic spectra with corresponding proportions of different compound contents under the premise of the first real sample thickness. Then, the first actual measurement spectrum actually detected by the first real sample is compared with the simulated spectrum library to obtain a target characteristic spectrum that is closest to the first actual measurement spectrum, as well as the Ta and C contents corresponding to the target characteristic spectrum in the simulated spectrum library. The Ta and C contents are the actual Ta and C contents in the TaC compound sample actually measured.

[0047] Since the epoxy resin material of substrate 1 contains C, in order to explore the influence of the C element in substrate 1 on the quantitative results, the analysis method further includes the following steps:

[0048] S07. Based on the actual Ta and C contents measured in step S06, the thickness of the substrate 1 in the TaC compound sample is maintained at a constant value D2, and the thickness of the target body 2 under the probe 101 varies between 100 nm and 1000 nm. Steps S02 and S03 are repeated, and a second relationship curve diagram between TaL / CK and the thickness of the target body 2, and / or TaM / CK and the thickness of the target body 2 is prepared.

[0049] Reference Figure 4 In the cross-sectional state of the TaC compound sample, it should be observed that the target body 2 has at least one inclined surface or gradually curved surface facing the substrate 1. When the probe 101 hits the TaC compound sample, it moves horizontally from one end of the inclined surface or gradually curved surface on the target body 2 to the other end along the cross-sectional surface of the TaC compound sample, thereby realizing the change of the thickness of the target body 2 under the probe 101.

[0050] S08. A third relationship curve diagram of TaL / CK and the thickness of the simulated TaC compound, and / or TaM / CK and the thickness of the simulated TaC compound, is obtained by computer simulation of a simulated TaC compound having a real Ta and C content and varying in thickness between 100 nm and 1000 nm. In the simulated state, the TaC compound does not have the substrate 1 and is therefore not affected by the C phase in the substrate 1.

[0051] S09, compare the second relationship curve graph with the third relationship curve graph, refer to Figure 5 , showing a comparison between the second relationship curve and the third relationship curve when measuring TaL / CK in an embodiment of the application (left) and a comparison between the second relationship curve and the third relationship curve when measuring TaL / CK (right), wherein the curve where the hollow triangle is located is the second relationship curve, and the curve where the solid triangle is located is the third relationship curve. The thickness of the target body 2 when the curves in the two relationship curves converge is selected as D3, when:

[0052] -10nm≤D1-(D2+D3)≤10nm

[0053] It was confirmed that the substrate 1 had no effect on the quantification of Ta and C.

[0054] In the embodiment of the present application, the target body 2 is hemispherical, the spherical surface of the target body 2 faces the substrate 1, and the diameter of the target body 2 is 4*e 6 nm. In step S04, the probe 101 of the X-ray spectrometer moves horizontally from the interface between the target 2 and the substrate 1 to the center of the target 2. A first relationship curve is prepared. At the same time, a fourth relationship curve is prepared between the thickness of the TaC compound sample and the horizontal movement distance of the probe 101. The fourth relationship curve is queried based on the critical thickness D1 to obtain the horizontal movement distance D4 of the probe 101, and the horizontal movement distance D4 of the probe 101 is determined to be 4*e with the center of the target 2 as the center. 6 In the region of nm-2D4 as the diameter, the measured TaL / CK and / or TaM / CK values ​​tend to be stable.

[0055] By measuring the area where the TaL / CK and / or TaM / CK values ​​on the TaC compound sample tend to be stable, when selecting the first real sample in step S06 , the implementer can quickly locate the correct insertion area of ​​the probe 101 , thereby improving quantitative efficiency.

[0056] Furthermore, in order to verify the accuracy of the actual Ta and C contents in the quantitative results, the analysis method further includes the following steps:

[0057] S10. Calculate the Ta and C contents using the Cliff-Lorimer factor calculation formula based on the X-ray spectrum peak intensities of TaL, TaM, and CK of the first authentic sample in step S06. Compare the true Ta and C contents with the calculated Ta and C contents. If the difference between the true Ta and C contents and the calculated Ta and C contents is less than 8%, the measured true Ta and C contents are determined to be accurate. By calculating the contents using a calculation method and comparing them with the actual contents measured using a fully quantitative method, the authenticity of the measurement results can be verified, ensuring the rigor of scientific research data.

[0058] Those skilled in the art will appreciate that while preferred embodiments of the present invention have been described, further variations and modifications may be made to these embodiments once those skilled in the art are aware of the underlying inventive concepts. Therefore, the appended claims are intended to be interpreted as encompassing the preferred embodiments and all variations and modifications that fall within the scope of the present invention. Clearly, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, the present invention is intended to encompass such modifications and variations as fall within the scope of the claims and their equivalents.

Claims

1. A multiphase Ta based on EDXs x C 1-x The fully quantitative analysis method is characterized in that The following steps are involved: S01. Prepare a TaC compound sample, wherein the TaC compound sample includes a substrate and a target, wherein the substrate is made of epoxy resin, and the target includes a TaC compound. The target is fixed on the top wall of the substrate, and the surface of the target is flush with the surface of the substrate; S02. collecting an actual measurement spectrum of the TaC compound sample by an X-ray spectrometer; S03. Analyze the actual measured spectrum to obtain a true sample of TaL / CK and / or TaM / CK values; S04. Changing the position at which the probe of the X-ray spectrometer is inserted into the TaC compound sample so that the thickness of the TaC compound sample under the probe varies between 100 nm and 1000 nm, repeating steps S02 and S03, and generating a first relationship curve between TaL / CK and TaC compound sample thickness, and / or TaM / CK and TaC compound sample thickness; S05. Determine, based on the first relationship curve, a critical thickness D1 of the TaC compound sample when the value of TaL / CK and / or TaM / CK tends to be stable; S06. Establish a simulated spectrum library of simulated characteristic spectra of different Ta and C contents in a TaC compound obtained by computer simulation, select a first real sample of the TaC compound sample under the probe whose thickness is not less than the critical thickness D1, compare a first actually measured spectrum corresponding to the first real sample with the simulated spectrum library to obtain a best-matched target characteristic spectrum, and determine that the Ta and C contents corresponding to the target characteristic spectrum are the actual Ta and C contents in the TaC compound sample; S07. Based on the measured actual Ta and C contents, the thickness of the substrate in the TaC compound sample is maintained at a constant value D2, and the thickness of the target under the probe is varied between 100 nm and 1000 nm. Steps S02 and S03 are repeated, and a second relationship graph of TaL / CK and target thickness, and / or TaM / CK and target thickness is generated. S08. A third relationship curve diagram of TaL / CK and thickness of the simulated TaC compound, and / or TaM / CK and thickness of the simulated TaC compound, when the thickness of the simulated TaC compound having actual Ta and C contents varies between 100 nm and 1000 nm by computer simulation; S09. Compare the second relationship curve diagram and the third relationship curve diagram, and select the target body thickness D3 when the curves in the two relationship curve diagrams converge. When: -10nm≤D1-(D2+D3)≤10nm It was determined that the substrate had no effect on the quantification of Ta and C; S10. Calculate the calculated Ta and C contents using the Cliff-Lorimer factor calculation formula based on the X-ray spectrum peak intensities of TaL, TaM, and CK of the first real sample described in step S06, and compare the true Ta and C contents with the calculated Ta and C contents. When it is determined that the difference between the true Ta and C contents and the calculated Ta and C contents is less than 8%, it is determined that the measured true Ta and C contents are accurate.

2. A multi-phase Ta based on EDXs according to claim 1 x C 1-x The fully quantitative analysis method is characterized in that In step S03, the actual measured spectrum is analyzed, including: According to the actual measured spectrum, the background maps of TaL, TaM and CK were drawn using casino software. After Gaussian fitting of the background maps of TaL, TaM and CK, the values ​​of TaL / CK and TaM / CK were determined based on the peak intensities of the X-ray spectra of TaL, TaM and CK in the background maps of TaL, TaM and CK.

3. The EDXs-based multiphase Ta according to claim 1 x C 1-x The fully quantitative analysis method is characterized in that The target body is hemispherical, the spherical surface of the target body faces the substrate, and the diameter of the target body is 4*e 6 nm; In step S04, the probe of the X-ray spectrometer moves horizontally and linearly from the interface between the target and the substrate toward the center of the target, and a first relationship curve is generated while simultaneously generating a fourth relationship curve between the thickness of the TaC compound sample and the horizontal movement distance of the probe; According to the critical thickness D1, the fourth relationship curve is searched to obtain the horizontal moving distance D4 of the probe, and the horizontal moving distance D4 of the probe is determined to be 4*e with the center of the target body as the center. 6 In the region of nm-2D4 as the diameter, the measured TaL / CK and / or TaM / CK values ​​tend to be stable.

Images