CN114295663B - Magnesium-based electron probe microbeam component analysis standard sample and preparation method thereof - Google Patents
Magnesium-based electron probe microbeam component analysis standard sample and preparation method thereof Download PDFInfo
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- 239000011777 magnesium Substances 0.000 title claims abstract description 184
- 239000000523 sample Substances 0.000 title claims abstract description 125
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 91
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000004458 analytical method Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000012360 testing method Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000703 high-speed centrifugation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 239000011159 matrix material Substances 0.000 abstract description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 16
- 239000011135 tin Substances 0.000 description 14
- 238000001514 detection method Methods 0.000 description 11
- 238000010894 electron beam technology Methods 0.000 description 10
- 238000004445 quantitative analysis Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000012937 correction Methods 0.000 description 7
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 6
- 230000001133 acceleration Effects 0.000 description 6
- 229910019021 Mg 2 Sn Inorganic materials 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 241001347978 Major minor Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- -1 oxides Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010972 statistical evaluation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
The invention discloses a magnesium-based electron probe microbeam component analysis standard sample and a preparation method thereof, belonging to the technical field of electron probe microbeam analysis. A preparation method of a magnesium-based electron probe microbeam component analysis standard sample is characterized by comprising the following steps of: the preparation method mainly comprises the following steps: s1, melting treatment: uniformly mixing high-purity Mg and high-purity Sb simple substance powder, sealing the Mg and Sb mixture by using a tantalum tube, then sealing the tantalum tube in a quartz glass tube, and then placing the quartz glass tube in a muffle furnace to perform high-temperature melting treatment at 850 ℃; s2, annealing treatment: and (3) carrying out annealing treatment on the Mg 3Sb2, and cooling the temperature from 850 ℃ to 650 ℃ at a speed of 2 ℃/h to enable the Mg 3Sb2 monocrystal to grow slowly. The Mg 3Sb2 monocrystal is used as a standard sample, so that the influence of matrix effect on the in-situ component analysis of the electron probe micro-region of the magnesium-based thermoelectric material can be effectively eliminated, and the method is mainly used for calibrating test data of the magnesium-based thermoelectric material and controlling the quality of the test process.
Description
Technical Field
The invention relates to the technical field of electron probe microbeam analysis, in particular to a magnesium-based electron probe microbeam component analysis standard sample and a preparation method thereof.
Background
The thermoelectric power generation or refrigeration device developed based on the technology has the advantages of simple structure, durability, no noise, no pollution and the like, and therefore, the thermoelectric power generation or refrigeration device has huge commercial application potential.
Classical room temperature commercial bismuth tellurium-based thermoelectric materials are limited in their large-scale application due to their poor mechanical properties and the need to use scarce and expensive tellurium elements. The binary magnesium-based thermoelectric materials Mg 2 Si and Mg 3XV 2(XV =Sb, bi which are emerging in recent years are prepared into the multielement magnesium-based thermoelectric material by doping elements (such as Ni, cu, zn, ge, ag, sn, pb and the like), and the multielement magnesium-based thermoelectric material has the remarkable advantages of equivalent thermoelectric performance and better mechanical toughness as bismuth telluride-based thermoelectric materials, rich raw materials, low price, low density and the like, so that the multielement magnesium-based thermoelectric material is expected to replace the traditional N-type room temperature thermoelectric material.
In order to further enhance the thermoelectric performance of the magnesium-based thermoelectric material, higher demands are put on the quality of the material and the corresponding synthesis means, including good homogeneity, strict regulation of the stoichiometric ratio, reproducibility, mass-producibility, and the like. The difficulty in achieving the above-mentioned object is mainly derived from the high chemical activity of magnesium (easy oxidation in air) and the high vapor pressure of magnesium above 600 ℃, so that the magnesium is usually formed into point defects of magnesium vacancies according to the normal stoichiometric ratio, and the excessive compensation of magnesium is formed into point defects of magnesium gaps.
The electron probe is a mature in-situ micro-region (micron-submicron level) major-minor element analysis technology, and the high accuracy of quantitative analysis is very suitable for measuring the stoichiometric ratio and the element surface distribution of the magnesium-based thermoelectric material. However, limited by the principles of the test method, high quality test data relies on calibration and analytical quality control using matrix matched standard samples.
The existing magnesium-containing microbeam analysis standard samples of metals (such as high-purity simple substance Mg), oxides (such as MgO), silicate minerals (such as forsterite, plagiopsinite and the like) and the like are not suitable for the analysis and test of magnesium-based thermoelectric materials due to the reasons of easy oxidization, unmatched matrixes and the like. Therefore, there is a need to develop suitable standard samples for micro-area component analysis and further research of such thermoelectric materials.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems existing in the prior art, the invention aims to provide a magnesium-based electron probe microbeam component analysis standard sample and a preparation method thereof, and the standard sample can effectively eliminate the influence of matrix effect on magnesium-based thermoelectric material electron probe micro-area in-situ component analysis in the magnesium-based thermoelectric material electron probe in-situ micro-area component analysis process, and can calibrate test data and control the quality of the test process.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
A preparation method of a magnesium-based electron probe microbeam component analysis standard sample is characterized by comprising the following steps of: the preparation method comprises the following steps:
s1, melting treatment:
Uniformly mixing high-purity Mg and high-purity Sb simple substance powder, sealing the Mg and Sb mixture by using a tantalum tube, then sealing the tantalum tube in a quartz glass tube, and then placing the quartz glass tube in a muffle furnace to perform high-temperature melting treatment at 850 ℃;
s2, annealing treatment:
annealing the Mg 3Sb2, and cooling the temperature from 850 ℃ to 650 ℃ at a speed of 2 ℃/h to slowly grow Mg 3Sb2 monocrystal;
s3, centrifugal separation:
Putting the quartz glass tube into a centrifuge for high-speed centrifugation to separate Mg 3Sb2 single crystals from Sb fluxing agents, thus obtaining layered Mg 3Sb2 single crystals;
s4, preparing a light sheet:
And preparing Mg 3Sb2 monocrystal into a light sheet with proper size, and evaporating a carbon film on the surface of the light sheet to obtain a standard sample suitable for micro-area in-situ component analysis by an electron probe method.
Preferably, the atomic molar ratio of Mg to Sb elemental powder is 3:7.
Preferably, mg and Sb elemental powders are uniformly mixed, the Mg and Sb mixture is sealed using a tantalum tube, and then the tantalum tube is sealed in a quartz glass tube, and these operations are all completed in an argon glove box.
Preferably, the purity of Mg is not less than 99.8%, and the granularity of Mg is 100-200 meshes; the purity of Sb is not lower than 99.999%, and the granularity of Sb is not lower than 200 meshes.
Preferably, the thickness of the prepared lamellar Mg 3Sb2 single crystal is 0.2-1.5mm, and the length is 3-5mm.
Preferably, the preparation process of the Mg 3Sb2 monocrystal into the light sheet comprises embedding the Mg 3Sb2 monocrystal into epoxy resin, and then carrying out rough grinding, fine grinding, polishing and ultrasonic cleaning on the Mg 3Sb2 monocrystal, so that the light sheet is flat and smooth in surface, free of pollution and free of scratches.
Preferably, a carbon film with a thickness of 20nm is deposited on the surface of the light sheet.
Preferably, the polished section is put into a vacuum drying oven for preservation immediately after the preparation of the polished section is completed.
Preferably, the magnesium-based electron probe microbeam component analysis standard sample is used for applying the prepared Mg 3Sb2 single crystal standard sample to the technical field of electron probe microbeam analysis, is mainly used for calibrating test data of magnesium-based thermoelectric materials and can also be used for controlling the quality of a test process.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
Compared with the existing magnesium-containing microbeam analysis standard samples of simple substance metals, oxides, silicate minerals and the like, the method can effectively eliminate the influence of matrix effect on magnesium-based thermoelectric material electronic probe micro-area in-situ component analysis by using the Mg 3Sb2 monocrystal as the standard sample of magnesium, and can well calibrate data and control test quality in the magnesium-based thermoelectric material electronic probe in-situ micro-area component analysis process.
Drawings
FIG. 1 is a diagram of a single crystal sample of layered Mg 3Sb2 of the present invention.
Detailed Description
Referring to fig. 1, a method for preparing a magnesium-based electron probe microbeam component analysis standard sample is characterized in that: the preparation method comprises the following steps:
s1, melting treatment:
Uniformly mixing high-purity Mg and high-purity Sb simple substance powder, sealing the Mg and Sb mixture by using a tantalum tube, then sealing the tantalum tube in a quartz glass tube, and then placing the quartz glass tube in a muffle furnace to perform high-temperature melting treatment at 850 ℃;
s2, annealing treatment:
annealing the Mg 3Sb2, and cooling the temperature from 850 ℃ to 650 ℃ at a speed of 2 ℃/h to slowly grow Mg 3Sb2 monocrystal;
s3, centrifugal separation:
Putting the quartz glass tube into a centrifuge for high-speed centrifugation to separate Mg 3Sb2 single crystals from Sb fluxing agents, thus obtaining layered Mg 3Sb2 single crystals;
s4, preparing a light sheet:
And preparing Mg 3Sb2 monocrystal into a light sheet with proper size, and evaporating a carbon film on the surface of the light sheet to obtain a standard sample suitable for micro-area in-situ component analysis by an electron probe method.
The atomic mole ratio of the Mg and Sb elemental powder is 3:7.
The simple substance powder of Mg and Sb are uniformly mixed, the mixture of Mg and Sb is sealed by using a tantalum tube, then the tantalum tube is sealed in a quartz glass tube, and all the operation processes are completed in an argon glove box so as to prevent magnesium from being rapidly oxidized in the air.
The purity of Mg is not lower than 99.8%, and the granularity of Mg is 100-200 meshes; the purity of Sb is not lower than 99.999%, and the granularity of Sb is not lower than 200 meshes.
The thickness of the prepared lamellar Mg 3Sb2 single crystal is 0.2-1.5mm, and the length is 3-5mm.
The process for preparing the Mg 3Sb2 monocrystal into the light sheet comprises embedding the Mg 3Sb2 monocrystal into epoxy resin, carrying out rough grinding, fine grinding, polishing and ultrasonic cleaning on the epoxy resin, and finally obtaining the light sheet with flat and smooth surface, no pollution and no scratch.
A carbon film with a thickness of 20nm is deposited on the surface of the polished section.
Placing the polished section immediately after the preparation and (5) storing in a vacuum drying oven.
A magnesium-based electron probe microbeam component analysis standard sample is used for applying the prepared Mg 3Sb2 single crystal standard sample to the technical field of electron probe microbeam analysis, is mainly used for calibrating test data of magnesium-based thermoelectric materials and can also be used for controlling the quality of a test process.
Electronic probe quantitative analysis generally uses ZAF method, PRZ method and standard curve method to correct test data, but is limited by the principle of method, high quality test data depends on standard sample matched with matrix for calibration and analysis quality control. For ease of discussion, the ZAF method is chosen for all embodiments.
A magnesium-based electron probe microbeam component analysis standard sample according to the present invention is further described below with reference to specific examples.
Example 1
Firstly, preparing Mg 2.983Ag0.017Sb2 single crystal into a light sheet with proper size according to the requirement of an electronic probe on a sample, evaporating a carbon film with the thickness of 20nm on the surface of the light sheet, wherein in the process of preparing the Mg 2.983Ag0.017Sb2 single crystal into the light sheet, the used liquid is absolute ethyl alcohol, so that the Mg 2.983Ag0.017Sb2 single crystal is prevented from contacting water;
step two, the prepared polished section is put on an electronic probe sample stage and is pushed to an electronic probe vacuum sample bin;
third, a series of quantitative analysis conditions such as an acceleration voltage, an electron beam current, a spectroscopic single crystal, a detector, a standard sample and the like are set, wherein the acceleration voltage is set to be 20kV, the electron beam current is set to be 2X 10 -8 A, quantitative analysis tests are carried out, and test results obtained by performing ZAF method calibration on Mg 2.983Ag0.017Sb2 single crystals by using different standard sample combinations (serial numbers 1-4) are shown in table 1.
TABLE 1 test results from calibration of Mg 2.983Ag0.017Sb2 single crystals using different standard sample combinations
Analysis of test results:
Standard values of mass percentages (wt.%) of magnesium, silver and antimony in the Mg 2.983Ag0.017Sb2 single crystal are 22.81%, 0.58% and 76.62%, respectively, and standard values of atomic mole ratios of magnesium, silver and antimony in the Mg 2.983Ag0.017Sb2 single crystal are 59.66:0.34:40.00.
When a single Mg substance or a single Mg 2 Si crystal is selected as a standard magnesium sample, the test result shows that the mass percent average value of the collected 11 detection points of Mg and the atomic mole ratio average value of the Mg deviate from the standard value obviously because of obvious atomic number effect (Z) and absorption effect (A) differences (Z, A, F are 1 respectively) between the single Mg 2.983Ag0.017Sb2 crystal.
When Mg 2 Sn single crystal is used as a standard sample of magnesium, the atomic number effect (Z) and the absorption effect (A) are obviously improved, but the test result and the standard value have non-negligible deviation.
The Mg 3Sb2 monocrystal is selected as a standard sample of magnesium and antimony, and the test result shows that the mass percent of the magnesium and the mass percent of the antimony in the Mg 2.983Ag0.017Sb2 monocrystal are very consistent with the standard value of the mass percent of the magnesium and the mass percent of the antimony in the Mg 2.983Ag0.017Sb2 monocrystal, and the atomic mole ratio average value of the magnesium and the antimony is also very consistent with the standard value of the atomic mole ratio of the magnesium and the antimony in the Mg 2.983Ag0.017Sb2 monocrystal, so that the Mg 3Sb2 monocrystal can effectively inhibit the influence of a matrix effect on the micro-area in-situ component analysis of the magnesium-based thermoelectric material electron probe.
Therefore, when quantitative analysis of electron probe is performed on ternary or multi-element solid solutions prepared by using Mg 3Sb2 single crystals as a matrix, mg 3Sb2 single crystals should be preferably used as standard samples of magnesium and antimony.
Example 2
Firstly, preparing MgAgSb polycrystal into a light sheet with proper size according to the requirement of an electronic probe on a sample, evaporating a carbon film with the thickness of 20nm on the surface of the light sheet, wherein in the process of preparing MgAgSb polycrystal into the light sheet, the used liquid is absolute ethyl alcohol, so as to avoid MgAgSb polycrystal from contacting water;
step two, the prepared polished section is put on an electronic probe sample stage and is pushed to an electronic probe vacuum sample bin;
Third, a series of quantitative analysis conditions such as an acceleration voltage, an electron beam current, a spectroscopic single crystal, a detector, a standard sample and the like are set, wherein the acceleration voltage is set to be 20kV, the electron beam current is set to be 2X 10 -8 A, quantitative analysis tests are carried out, and test results obtained by carrying out ZAF method calibration on MgAgSb polycrystal by using different standard sample combinations (serial numbers 1-4) are shown in table 2.
TABLE 2 test results from calibration of MgAgSb polycrystals using different standard sample combinations
Analysis of test results:
Standard values of mass percentages (wt.%) of magnesium, silver and antimony in MgAgSb polycrystal are 9.57%, 42.48% and 47.95%, respectively, and standard values of atomic mole ratios of magnesium, silver and antimony in MgAgSb polycrystal are 33.33:33.33:33.33 (i.e., 1:1:1).
When a single Mg substance or a single Mg 2 Si crystal is selected as a standard magnesium sample, the test result shows that the mass percent content average value of the collected 11 detection points and the atomic mole ratio average value of the Mg deviate from the standard value obviously because of obvious atomic number effect (Z) and absorption effect (A) differences (Z, A, F are 1 respectively) between the single Mg substance and the single Mg 2 Si crystal and MgAgSb polycrystal.
When Mg 2 Sn single crystal is used as a standard sample of magnesium, the atomic number effect (Z) and the absorption effect (A) are obviously improved, but the test result and the standard value have non-negligible deviation.
The Mg 3Sb2 single crystal is selected as a standard sample of magnesium and antimony, and the test result shows that the mass percent average value of the magnesium and the antimony in the 11 collected detection points is basically consistent with the mass percent standard value of the magnesium and the antimony in the MgAgSb polycrystal, and the atomic mole ratio average value of the magnesium and the antimony in the 11 detection points is basically consistent with the atomic mole ratio standard value of the magnesium and the antimony in the MgAgSb polycrystal, so that the Mg 3Sb2 single crystal can effectively inhibit the influence of a matrix effect on the micro-area in-situ component analysis of the magnesium-based thermoelectric material electron probe.
Since the multi-single crystal system often has the phase separation phenomenon, the prepared MgAgSb polycrystal sample contains fine-grained Mg: ag: the Sb atomic ratio may deviate from 1:1:1.
Therefore, in the absence of MgAgSb single crystal standard, mg 3Sb2 single crystal should be preferred as standard sample of magnesium and antimony when quantitative analysis of electron probe is performed on MgAgSb polycrystal or multi-element solid solution prepared by taking it as matrix.
Example 3
Firstly, preparing Mg 2Si0.214Sn0.786 single crystal into a light sheet with proper size according to the requirement of an electronic probe on a sample, evaporating a carbon film with the thickness of 20nm on the surface of the light sheet, wherein in the process of preparing the Mg 2Si0.214Sn0.786 single crystal into the light sheet, the used liquid is absolute ethyl alcohol, so that the Mg 2Si0.214Sn0.786 single crystal is prevented from contacting water;
step two, the prepared polished section is put on an electronic probe sample stage and is pushed to an electronic probe vacuum sample bin;
Third, a series of quantitative analysis conditions such as an acceleration voltage, an electron beam current, a spectroscopic single crystal, a detector, a standard sample and the like are set, wherein the acceleration voltage is set to be 20kV, the electron beam current is set to be 2X 10 -8 A, quantitative analysis tests are carried out, and test results obtained by performing ZAF method calibration on Mg 2Si0.214Sn0.786 single crystals by using different standard sample combinations (serial numbers 1-4) are shown in Table 3.
TABLE 3 test results from calibration of Mg 2Si0.214Sn0.786 single crystals using different standard sample combinations
Analysis of test results:
Standard values of mass percentages (wt.%) of magnesium, silicon and tin in the Mg 2Si0.214Sn0.786 single crystal are 32.87%, 4.06% and 63.07%, respectively, and standard values of atomic mole ratios of magnesium, silicon and tin in the Mg 2Si0.214Sn0.786 single crystal are 66.67:7.13:26.20.
When a single Mg substance or a single Mg 2 Si crystal is selected as a standard magnesium sample, the test result shows that the mass percent content average value of the collected 11 detection points Mg and the atomic mole ratio average value of the Mg deviate from the standard value obviously because the single Mg substance or the single Mg 2 Si crystal has obvious atomic number effect (Z) and absorption effect (A) difference (Z, A, F is 1 and represents complete matrix matching) with the single Mg 2Si0.214Sn0.786 crystal.
When Mg 2 Sn or Mg 3Sb2 monocrystal is selected as a standard sample of magnesium, the atomic number effect (Z) and the absorption effect (A) are obviously improved, and the test result shows that the mass percent average value of the magnesium is basically consistent with the mass percent standard value of Mg 2Si0.214Sn0.786 monocrystal magnesium, and the atomic mole ratio average value of the magnesium is basically consistent with the atomic mole ratio standard value of the magnesium in the Mg 2Si0.214Sn0.786 monocrystal.
Although the calibration effect of the standard sample of Mg 2 Sn single crystal is better than that of the standard sample of Mg 3Sb2 single crystal, the matrix of the standard sample is more matched with the standard sample of Mg 2Si0.214Sn0.786, and the standard sample of Mg 3Sb2 single crystal is also a good choice when the quantitative component analysis of an electronic probe is carried out on the standard sample of Mg 2Si1-xSnx single crystal or a multi-element solid solution prepared by taking the standard sample of Mg 2 Sn single crystal as a matrix.
Wherein,
ZAF correction formula profile:
In the above formula, UNK and STD refer to an unknown sample and a standard sample, and G Z、GA and G F are an atomic number correction coefficient (Z), an absorption correction coefficient (a), and a fluorescence correction coefficient (F), respectively, and are abbreviated as ZAF correction method.
The final purpose of the correction is to eliminate matrix effects between the unknown and standard samples, i.e. differences in the behavior of the incident electron beam in the sample, the absorption of characteristic X-rays in the sample, and secondary fluorescent X-ray excitation.
In the practical application process, due to the complexity of the material structure and components and various errors introduced by the approximate calculation of various physical parameters (such as mass absorption coefficient, backscattering factor, permeability factor and the like) in the formula, the ZAF correction method cannot completely eliminate the matrix effect difference between an unknown sample and a standard sample in many cases, so that the standard sample matched with the matrix should be preferentially selected for obtaining high-quality electronic probe test data.
Uniformity and stability analysis was performed on layered Mg 3Sb2 single crystals as follows:
according to the specification of uniformity detection of a standard sample in GB/T4930-2021 technical condition rules for micro-beam analysis of a standard sample by a micro-beam analysis electron probe, 10 pieces of single crystal particles of more than 200 pieces of layered Mg 3Sb2 are randomly selected for uniformity detection of the standard sample. According to the requirements of an electron probe on a sample, sequentially placing the selected layered Mg 3Sb2 single crystals with the exposed surface (ab surface) upwards, coating the Mg 3Sb2 single crystals with epoxy resin, then carrying out rough grinding, fine grinding, polishing and ultrasonic cleaning, preparing an epoxy resin polished section with the diameter of 25.4mm, evaporating a carbon film with the thickness of 20nm on the surface of the epoxy resin polished section, using absolute ethyl alcohol in the preparation process to avoid contacting water, setting a series of experimental analysis conditions such as an accelerating voltage, an electron beam current, a beam splitting single crystal, a detector and the like, wherein the accelerating voltage is set to be 20kV, the electron beam current is set to be 2X 10 -8 A, the peak position test time of Mg and Sb is respectively set to be 50s and 20s (the total count is not less than 1000000), and carrying out analysis test by using an electron beam focusing mode.
Before the non-uniformity detection, 5Mg 3Sb2 single crystal particles are randomly selected, 10 points are randomly measured on the edge and the inside of each particle, and the result shows that no significant difference exists between the Mg and Sb contents at the edge and the inside of the particle. For each particle, 7 points were randomly selected, and 3X-ray counts were acquired and recorded for each point. The particles were analyzed in a random order, with each particle analyzed twice and each analysis in a different order. Therefore, the number of points for uniformity detection is 420, and the result of the statistical evaluation and calculation of the non-uniformity data shows that the relative uncertainty of the average content of Mg and Sb in the 95% confidence interval is 1.24% and 1.79% respectively, and the samples are uniform and meet the uniformity requirement as a standard sample. In addition, in order to detect the content trend of elements in particles, 5 particles are randomly selected, two mutually perpendicular detection lines are used for carrying out line detection with the point spacing of 5 mu m and the length of 200 mu m, and the result shows that the concentration change is within a 99% confidence limit, which indicates that the content trend of Mg and Sb does not exist.
The above-mentioned optical sheets were subjected to 3 sampling analysis using an electron probe for 3 months, and the RSD% values of Mg and Sb were counted. The precision of the measurement result is similar to that of the analysis method, so that the prepared lamellar Mg 3Sb2 monocrystal is considered to be stable.
Claims (6)
1. A preparation method of a magnesium-based electron probe microbeam component analysis standard sample is characterized by comprising the following steps of: the preparation method comprises the following steps:
s1, melting treatment:
Uniformly mixing high-purity Mg and high-purity Sb simple substance powder, sealing the Mg and Sb mixture by using a tantalum tube, then sealing the tantalum tube in a quartz glass tube, and then placing the quartz glass tube in a muffle furnace to perform high-temperature melting treatment at 850 ℃;
s2, annealing treatment:
annealing the Mg 3Sb2, and cooling the temperature from 850 ℃ to 650 ℃ at a speed of 2 ℃/h to slowly grow Mg 3Sb2 monocrystal;
s3, centrifugal separation:
Putting the quartz glass tube into a centrifuge for high-speed centrifugation to separate Mg 3Sb2 single crystals from Sb fluxing agents, thus obtaining layered Mg 3Sb2 single crystals;
s4, preparing a light sheet:
Preparing Mg 3Sb2 monocrystal into a light sheet with proper size, and evaporating a carbon film on the surface of the light sheet to obtain a standard sample suitable for micro-area in-situ component analysis by an electronic probe method;
The process for preparing the Mg 3Sb2 monocrystal into the light sheet comprises embedding the Mg 3Sb2 monocrystal into epoxy resin, and then carrying out rough grinding, fine grinding, polishing and ultrasonic cleaning on the Mg 3Sb2 monocrystal to obtain the light sheet with smooth and flat surface, no pollution and no scratch;
in the process of preparing Mg 3Sb2 monocrystal into a light sheet, the liquid used is absolute ethyl alcohol;
the thickness of the vapor deposition carbon film is 20nm;
Placing the polished section immediately after the preparation and (5) storing in a vacuum drying oven.
2. The method for preparing the magnesium-based electron probe microbeam component analysis standard sample according to claim 1, which is characterized in that: the atomic mole ratio of the Mg and Sb elemental powder is 3:7.
3. The method for preparing the magnesium-based electron probe microbeam component analysis standard sample according to claim 1, which is characterized in that: the simple substance Mg and Sb powder are uniformly mixed, the mixture Mg and Sb is sealed by using a tantalum tube, then the tantalum tube is sealed in a quartz glass tube, and all the operation processes are completed in an argon glove box.
4. The method for preparing the magnesium-based electron probe microbeam component analysis standard sample according to claim 1, which is characterized in that: the purity of Mg is not lower than 99.8%, and the granularity of Mg is 100-200 meshes; the purity of Sb is not lower than 99.999%, and the granularity of Sb is not lower than 200 meshes.
5. The method for preparing the magnesium-based electron probe microbeam component analysis standard sample according to claim 1, which is characterized in that: the thickness of the prepared lamellar Mg 3Sb2 single crystal is 0.2-1.5mm, and the length is 3-5mm.
6. A magnesium-based electron probe microbeam component analysis standard sample is characterized in that: the method for preparing the Mg 3Sb2 single crystal standard sample is applied to the technical field of electron probe microbeam analysis, is mainly used for calibrating test data of magnesium-based thermoelectric materials and can also be used for controlling the quality of a test process.
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