3D printing of solid analytical reference materials and its application in situ quantitative analysis method

Abstract

The present invention refers to a method for preparing solid analytical standard reference materials using 3D printing technology and an in-situ quantitative analysis method using the same, including: standard sample preparation: preparing a series of standard solutions with varying concentration gradients, adding different volumes of standard solutions into a ball mill, mixing them with a base powder under the action of a dispersant and cellulose to form a printing slurry, and obtaining the slurry after 3D printing, molding, drying, and degreasing. Quantitative calibration curve drawing: using the actual content of doping elements in the standard sample quantitatively measured by ICP-MS / AES as the horizontal coordinate, and using the response signal of the doping elements in the standard sample measured by LA-ICP-MS as the vertical coordinate. Doping element content analysis: performing LA-ICP-MS detection on the sample to be tested, and analyzing the content of the doping elements in the sample to be tested. The present invention adopts direct writing 3D printing technology with the advantages of simple sample preparation process, less pollution, good homogeneity, fast printing speed, and controllable sample size, thereby realizing quantitative analysis of the sample to be tested and improving analysis accuracy and efficiency.

Description

Technical Field

[0001] The present invention belongs to the technical field of analytical chemistry, and in particular relates to a method for preparing solid analytical standard reference materials using 3D printing technology and a method for in-situ quantitative analysis of the content of doping elements in solid samples using the same. Background Art

[0002] The conventional method for determining trace elements involves sample digestion followed by analysis using inductively coupled plasma mass spectrometry (ICP-MS) and spectroscopy. However, commercial crystalline samples are typically prepared with meticulous care and are of high application value, so sampling should be minimally destructive. This means that digestion, as a destructive and contaminating pretreatment method, is unsuitable for these samples. Furthermore, wet digestion only yields average values ​​for the sample being analyzed. LA-ICP-MS, as a direct, rapid, and highly sensitive technique for analyzing solid samples, has been widely used in fields such as glass, ceramics, and semiconductors. However, the lack of matrix-matched solid reference standards often hinders in situ quantitative analysis of these samples. Therefore, the development of relatively simple and rapid standard preparation methods is crucial for further promoting the application of LA-ICP-MS in materials analysis. Currently, various methods have been developed for preparing LA-ICP-MS microanalysis standards. Powder compaction is one of the oldest sample preparation techniques for in situ analysis. Other methods include fusion, dry droplet, and resin embedding, each with its own advantages, disadvantages, and scope of application.

[0003] As a standard material for direct solid injection analysis, uniformity of content distribution is a key performance indicator. Powder pressing, molten glass, and dry drop methods all suffer from drawbacks such as lengthy preparation steps that can easily lead to elemental contamination; poor sample homogeneity that results in insufficient analytical precision; high-temperature preparation conditions that cause element volatilization; and the addition of additives that dilute the sample and reduce elemental detection capabilities. Therefore, a faster and more accurate standard sample preparation method is needed for in-situ analysis of bulk samples. Summary of the Invention

[0004] In one aspect, the present invention provides a method for preparing solid analytical standard reference materials using 3D printing technology, which has the advantages of simple sample preparation process, less pollution, good homogeneity, fast printing speed, and controllable sample size.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing solid analytical standard reference material using 3D printing technology, comprising the steps of:

[0007] A high-concentration standard solution of the element to be measured is prepared and mixed with the matrix powder. Through the dispersing effect of the dispersant on the powder and the thickening effect of the thickener, a printing slurry with high solid content and low shear viscosity is formulated. The obtained printing slurry is 3D printed, dried and degreased to obtain a standard reference material for in-situ quantitative analysis of the matching matrix.

[0008] In some technical solutions, the preparation of a high concentration standard solution of the element to be measured is specifically as follows:

[0009] A high concentration standard solution with a concentration of 1000-10000 mg / kg is prepared by dissolving the metal powder or metal oxide powder of the element to be tested in HCl or HNO3.

[0010] In some technical solutions, the dispersant is a cationic wetting and dispersing agent or an anionic wetting and dispersing agent; and / or,

[0011] The thickener is thermally decomposable cellulose.

[0012] In some technical solutions, the dispersant is added at a concentration of 0.5-0.8 wt %; and

[0013] The added concentration of the thickener is 0.4-0.55 wt%.

[0014] In some technical solutions, the steps of 3D printing the obtained printing slurry are as follows:

[0015] Adding the obtained printing slurry into a syringe and printing the slurry on a glass substrate using a direct-write 3D printer, wherein the syringe pressure is adjusted between 16 psi and 26 psi according to the continuous extrusion state; and / or,

[0016] The drying step is carried out in a constant temperature and humidity chamber before the printing slurry is hydrated; and / or,

[0017] Described degreasing step is:

[0018] The dried green body was heated to 700°C at a rate of 1°C / min and kept at this temperature for 6 hours to remove the doped organic matter.

[0019] On the other hand, the present invention further provides a method for in situ quantitative analysis of the content of doping elements in solid samples. The former method is used to prepare a series of standard samples with gradient changes in the content of doping elements, and solid analysis and detection are carried out in LA-ICP-MS. A quantitative calibration curve is drawn, and then the content of the doping elements in the sample to be tested is analyzed. The analysis results are accurate and the analysis efficiency is improved.

[0020] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0021] A method for in-situ quantitative analysis of the content of doping elements in solid samples,

[0022] A series of standard samples with varying doping element contents were prepared using the above-mentioned method for preparing solid analytical standard reference materials using 3D printing technology;

[0023] A quantitative calibration curve is drawn with the actual content of the doping element in the standard sample quantitatively measured by inductively coupled plasma mass spectrometry or inductively coupled plasma atomic emission spectrometry as the abscissa and the response signal of the doping element in the standard sample measured by laser ablation inductively coupled plasma mass spectrometry as the ordinate;

[0024] Laser ablation inductively coupled plasma mass spectrometry is performed on the sample to be tested, and the content of the doping element in the sample to be tested is analyzed.

[0025] In some technical solutions, in situ quantitative analysis, the prepared standard sample is used as the external reference material, and the matrix element is used as the internal reference material. After correction of the relative sensitivity factor, the content of the doping element in the sample to be tested is calculated.

[0026] The calculation formula of the relative sensitivity factor is: RSF = Intensity (i) × Concentration (is) / Intensity (is) × Concentration (i).

[0027] In some technical solutions, the number of standard samples prepared is 4-5.

[0028] In some technical solutions, the laser ablation inductively coupled plasma mass spectrometry adopts a point scanning or line scanning method to detect the response signal intensity of the doping elements at different positions on the standard sample and the sample to be tested; and / or,

[0029] The laser ablation adopts a laser wavelength of 213 nm, a laser energy of 40%, a laser ablation aperture of 80 μm and a scanning rate of 70 μm / s.

[0030] In some technical solutions, in the quantitative calibration curve, the linear relationship between the actual content of the doping element and the response signal intensity is above 0.9996.

[0031] In some technical solutions, the error between the measured content value of the doping element in the solid sample and the reference value of the corresponding element obtained by wet digestion is between 0.26% and 9.72%.

[0032] The present invention adopts the above technical solution to have at least the following beneficial effects:

[0033] 1. This case utilizes direct ink writing (DIW) technology to prepare solid analytical standard reference materials. This 3D printing technology offers advantages such as simple sample preparation, minimal contamination, good homogeneity, fast printing speed, and controllable sample size. It overcomes the drawbacks of poor powder tableting uniformity and element loss during high-temperature melting.

[0034] 2. In this case, after preparing a high-concentration standard solution of the doping element, the element to be tested is quickly and evenly incorporated into the base powder in liquid form. Printing is then performed to obtain a block of standard reference material with a uniform distribution of elements. This block is suitable for high-throughput analysis using in-situ analytical techniques such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), laser induced breakdown spectroscopy (LIBS), or X-ray fluorescence (XRF).

[0035] 3. In this case, a dispersant is added during the mixing process of the high-concentration standard solution of the element to be measured and the matrix powder. Since the dispersant is adsorbed on the surface of the particles, the original particle surface is partially or completely covered by the dispersant, which prevents particle agglomeration and improves the suspension and stability of the slurry.

[0036] 4. In this case, cellulose is introduced during the mixing process of the high-concentration standard solution of the element to be measured and the matrix powder, which helps to improve the plasticity of the slurry. It increases the possibility of high solid content in the slurry without affecting the shear fluidity of the slurry printing. In addition, the cellulose can be completely removed by pyrolysis, which can minimize the introduction of impurity ions in the standard reference material.

[0037] 5. In this case, a series of standard samples with gradient variations in doping element content were prepared, and solid analysis and testing were carried out in LA-ICP-MS. A quantitative calibration curve was drawn, and then the content of the doping element in the sample to be tested was analyzed. The analysis results were accurate and the analysis efficiency was improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings and their symbols 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.

[0039] Figure 1 Schematic diagram of the distribution uniformity of the Y element in the BaCO3 reference material containing 0.875 mL of the spiked solution;

[0040] Figure 2 is the calibration curve of element Y in BaF2 crystal obtained by optimizing instrument parameters;

[0041] Figure 3Schematic diagram of the uniformity of distribution of multiple elements in BaCO3 reference material containing 6.890 g of spiked solution;

[0042] Figure 4 The calibration curves of multiple elements in BaCO3 samples were obtained by optimizing instrument parameters. DETAILED DESCRIPTION

[0043] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application. The various commonly used reagents used in the examples are all commercially available products.

[0044] The term "and / or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.

[0045] According to one embodiment of the present invention, a method for preparing a solid analytical standard reference material using 3D printing technology includes the following specific steps:

[0046] Preparation of standard solution: Dissolve the metal powder (such as Cu, Fe) or metal oxide powder (such as Dy2O3, Er2O3) of the element to be tested in a minimum amount of HCl or HNO3, and then use 1% HCl or HNO3 to make a high concentration standard solution with a concentration of 1000-10000 mg / kg.

[0047] Preparation of printing slurry: weigh the homemade high-concentration standard solution into a ball mill, add the dispersant into the ball mill, stir evenly, then gradually add the base powder and cellulose, mix and centrifuge for use.

[0048] Preparation of standard substances: The obtained printing slurry is added to a syringe, printed on a glass substrate using a direct-write 3D printer, dried in a constant temperature and humidity chamber, and then sintered and kept warm in a muffle furnace.

[0049] In this embodiment, adding dispersants and cellulose to the prepared slurry can effectively increase the solid content and reduce the slurry viscosity, so that the printed block standard has good shape retention and effectively improves the uneven distribution of the elements to be measured in the direct powder sample addition.

[0050] Dispersants mainly rely on steric effects and electrostatic effects to disperse the slurry. Particles in water are mainly affected by the following four forces: gravity, buoyancy, particle / water interfacial tension and interaction between particles, which makes the particles easy to settle and the slurry stability deteriorates. After the dispersant is added, the dispersant is adsorbed on the surface of the particles, and the original particle surface is partially or completely covered by the dispersant, which hinders particle agglomeration and improves the suspension and stability of the slurry.

[0051] The initial method to improve the plasticity of the slurry is to add clay or other additives. For standard reference materials, the introduction of impurity ions should be avoided as much as possible, so organic additives such as cellulose are more suitable for consideration because they can be completely removed by heat treatment. The thickening effect of cellulose on ceramic slurry is mainly achieved through swelling. On the one hand, hydrogen bonds are formed between cellulose and water molecules. The chemical adsorption of water in the amorphous region and the physical adsorption of water in the pore structure limit the movement of free water in the slurry. On the other hand, the volume of cellulose increases due to expansion, squeezing the powder particles to reduce the distance between them, thereby increasing the viscosity of the slurry. The addition of cellulose further increases the possibility of a high solid content in the slurry without affecting the shear fluidity of the slurry printing, significantly improving the printability of the slurry.

[0052] In a preferred embodiment, the dispersant is a cationic electrolyte, such as polyethyleneimine (PEI) or an anionic electrolyte, such as polyammonium acrylate (PAANH4). The present invention uses polyacrylic acid Dolapix CE-64 as a dispersant and hydroxyethyl cellulose (HEC) as a thickener.

[0053] In another preferred embodiment, by optimizing the spiked solution and base powder content, the concentrations of the dispersant and cellulose are selected to be 0.5-0.8 wt% and 0.4-0.55 wt%, respectively, to obtain a printing slurry with shear-thinning properties. At the same time, the injection pump air pressure is adjusted between 16 psi and 26 psi according to the continuous extrusion state, the inner diameter of the printing needle is selected to be 1.11 mm, the needle movement speed is 3 mm / s, and the line spacing is 1.5 mm.

[0054] The prepared slurry has a dispersant concentration of approximately 0.5 wt%. If the dispersant concentration is too low, it will be difficult to disperse a high-solids powder, and the resulting slurry green body will experience significant sintering shrinkage. Excessive dispersant addition can lead to elemental dilution, and excessive organic matter can affect inductively coupled plasma mass spectrometry (ICP-MS) detection.

[0055] In the prepared slurry, the mass concentration of cellulose is about 0.4-0.5wt%. If the concentration of cellulose is too low, the adsorption of free water will be reduced, resulting in poor lubrication between powder particles and increased friction between particles; if the concentration of cellulose is too high, more organic matter is added, the slurry viscosity is high and shear thickening occurs, the slurry dispersion process cannot effectively disintegrate the agglomerates, the powder dispersibility and the particle packing density in the blank are poor, and it may even be unusable for printing. Therefore, under the premise of effectively improving the printability of the slurry, the amount of cellulose should be as low as possible. For slurries with much higher cellulose additions, the bubbles in the slurry are difficult to remove, resulting in pores in the blank after the cellulose is thermally decomposed during the degreasing process.

[0056] In a preferred embodiment, to minimize the impact of hydration on the rheological properties of the slurry, printing and drying are completed before the slurry hydrates. To prevent deformation and cracking of the green body during drying, the sample is placed in a constant temperature and humidity chamber. After drying for 72 hours, the green body is heated to 700°C at a rate of 1°C / min and held at this temperature for 6 hours to remove organic matter.

[0057] According to another embodiment of the present invention, a method for in-situ quantitative analysis of the content of doping elements in a solid sample includes the following specific steps:

[0058] Preparation of standard samples: A series of high-concentration standard solutions with varying concentration gradients were prepared according to the method described in the previous example. Different volumes of standard solutions were added to a ball mill and mixed with the base powder in the presence of a dispersant and cellulose to form a printable slurry. The resulting printing slurry was added to a syringe and printed onto a glass substrate using a direct-write 3D printer. After drying in a constant temperature and humidity chamber, it was sintered and insulated in a muffle furnace. The amount of standard solution added ranged from 0.00875 mL to 8.75 mL, resulting in printing slurries with varying concentration gradients and uniform elemental distribution.

[0059] Quantitative calibration curve drawing: The quantitative calibration curve is drawn with the actual content of the doping element in the standard sample quantitatively measured by inductively coupled plasma mass spectrometry or inductively coupled plasma atomic emission spectrometry as the horizontal axis and the response signal of the doping element in the standard sample measured by laser ablation inductively coupled plasma mass spectrometry as the vertical axis.

[0060] Analysis of doping element content: The sample to be tested is subjected to laser ablation inductively coupled plasma mass spectrometry detection to analyze the content of doping elements in the sample to be tested.

[0061] This application uses a printed reference material as the external standard and the matrix element as the internal standard. The actual concentration of the standard sample obtained by ICP-MS / AES is used as the horizontal axis, and the response signal of the element to be measured is used as the vertical axis. The mass concentration of the element to be measured in the sample is extrapolated using a combination of internal and external standards.

[0062] In a preferred embodiment, in the in situ quantitative analysis, the prepared standard sample is used as the external reference material, the matrix element is used as the internal reference material, and the content of the doping element in the sample to be tested is calculated after correction by the relative sensitivity factor, wherein the calculation formula of the relative sensitivity factor is: RSF = Intensity (i) × Concentration (is) / Intensity (is) × Concentration (i).

[0063] In this example, a series of standard solutions of the element being tested were prepared at varying concentrations, thereby preparing a series of printing pastes at varying concentrations. According to the method of the present invention, more accurate results can be obtained by preparing fewer spiked printing pastes with varying concentration gradients. For example, the number of reference substances printed at varying concentrations can be 4-5.

[0064] In a preferred embodiment, laser ablation inductively coupled plasma mass spectrometry (LAIPS) employs point scanning or line scanning to detect the response signal intensity of the doping element at different locations on the standard sample and the sample to be tested, ensuring uniformity of the standard sample. Specifically, 20 random ablation cycles are performed on each sample. Laser ablation utilizes a laser wavelength of 213 nm, a laser energy of 40%, an ablation aperture of 80 μm, and a scan rate of 70 μm / s. Within this range, the response signal exhibits high sensitivity and good stability, and the ablation pits have good morphology.

[0065] The standard reference materials prepared in this case have concentrations of the elements to be measured at either the mg / kg or wt% level, making them suitable for trace analysis using highly sensitive instruments such as LA-ICP-MS, as well as major element analysis using instruments such as LIBS / XRF.

[0066] The following examples are further given to illustrate the present invention in detail. It should be understood that the following examples are only used to further illustrate the present invention and cannot be interpreted as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the scope of protection of the present invention. The specific concentrations, temperatures, reagents, etc. of the following examples are only examples of suitable ranges, and those skilled in the art can make selections within the appropriate range through the description herein, and are not limited to the specific numerical values ​​exemplified below.

[0067] Instrument parameters: Laser ablation used an NWR 213nm Nd-YAG laser ablation sampling system with a laser wavelength of 213nm, a laser energy of 40%, a laser frequency of 20Hz, an ablation aperture of 80μm, a scan rate of 35μm / s, and a helium flow rate of 0.7L / min; the ICP-MS was a Thermo iCAPQ quadrupole, helium was used as the carrier gas, and the argon flow rate was 0.7L / min.

[0068] Example 1: Preparation of Y-doped BaCO3 matrix standard reference material

[0069] 0.00875mL, 0.0875mL, 0.875mL, 1.75mL, and 8.75mL of a homemade high-concentration standard solution of element Y were weighed into a reagent bottle, and 0.3g of CE-64 dispersant was added. After stirring, 27.85g of BaCO3 matrix powder was added. After centrifugation, 0.2g of HEC cellulose was added and centrifuged again. A printing slurry with high solid content and low viscosity was prepared. The slurries of five concentrations were loaded into disposable syringes and printed using a direct-write 3D printer. The resulting block samples were slowly evaporated in a constant temperature and humidity chamber for 72 hours and then degreased in a muffle furnace at a temperature programmed at 1°C / min to 700°C for 6 hours.

[0070] A series of standard reference materials doped with Y at different concentrations in BaCO3 matrix were prepared. 20 random ablation lines in LA-ICP-MS showed the uniform distribution of each element. Figure 1 , and establish a calibration curve see Figure 2 The calibration curve uses the actual concentration of each element in the reference material determined by ICP-MS / AES as the horizontal axis and the signal intensity of the element to be measured normalized to the internal standard element as the vertical axis. The actual content of the element to be measured in the sample is deduced based on the intensity ratio of the element to be measured and the internal standard element in the stripping analysis sample. When the Y element was doped in three BaF2 crystals using BaCO3 matrix as the external standard, the linear equation of the calibration curve was Y=1086.6X+60982, and the linear R 2 =0.9996. The CPS(Y / Ba) values ​​for the three BaF2 crystals were 6.658, 5.553, and 4.296, respectively. The Y content in the three BaF2 crystals calculated using this protocol is essentially consistent with the quantitative values ​​obtained by wet digestion ICP-AES, demonstrating the reliability of this protocol (see Table 1). The LA-ICP-MS and ICP-AES data in Table 1 are based on three replicate experiments.

[0071] Example 2: Preparation of BaCO3 matrix standard reference material doped with various trace elements

[0072] 6.89g of the prepared multi-element standard solution was weighed into a reagent bottle. 0.32g of CE-64 dispersant was added and stirred thoroughly. BaCO3 powder was then added to the reagent in multiple batches, stirring thoroughly and then adding again. The amounts added were 5.02g, 5.09g, 6.33g, 6.04g, and 5.26g, respectively. The powder was dispersed and centrifuged, and 0.23g of HEC cellulose was added. After mechanical stirring, the mixture was centrifuged again to mix thoroughly. The prepared slurry was transferred to a disposable syringe and fixed to a direct-write 3D printing platform. An air pump was connected to the syringe and the slurry was continuously extruded at 22psi. The printing needle had an inner diameter of 1.11mm, a needle travel speed of 3mm / s, and a line spacing of 1.5mm. The printed sample was slowly dried in a constant temperature and humidity chamber and then degreased in a muffle furnace at a temperature programmed at 1°C / min to 700°C for 6h.

[0073] When analyzing multiple doping elements in BaF2 ceramic wafers with unknown concentrations using BaCO3 matrix as external standard, 20 random ablation lines in LA-ICP-MS indicate the uniform distribution of each element, see Figure 3 ; and establish a calibration curve with a linear coefficient of 0.9960-0.9999 from Fe to Yb, see Figure 4 The calculated contents of 15 elements in the BaF2 sample obtained by this scheme are basically consistent with the quantitative values ​​obtained by wet digestion ICP-AES, which proves the reliability of this scheme. See Table 2. The LA-ICP-MS data and ICP-AES data in Table 2 are the results of three repeated experiments.

[0074] Table 1. Quantitative determination of Y-doped standard samples and analysis results of the elements in actual samples

[0075]

[0076] Table 2. Quantitative determination of the elements in actual samples by doping standard samples with multiple trace elements

[0077]

[0078] In summary, the 3D printing standard reference material preparation method provided by the present invention reduces the sample preparation procedures, avoids cross contamination to the greatest extent, improves the uniformity of element distribution, and can accurately analyze and detect actual samples.

[0079] Without departing from the purpose of the basic characteristics of the present invention, the present invention can be embodied in various forms. Therefore, the implementation method of the present invention is used for illustration rather than limitation. Since the scope of the present invention is limited by the claims rather than the description, all changes that fall within the scope defined by the claims or the equivalent range of the scope defined by them should be understood to be included in the claims.

Claims

1. A method for preparing solid analytical standard reference materials using 3D printing technology, characterized in that: Including steps: A high concentration standard solution of 1000-10000 mg / kg is prepared by dissolving the metal powder or metal oxide powder of the element to be tested in HCl or HNO3; The high-concentration standard solution is mixed with a base powder, a dispersant, and pyrolyzable cellulose in mass fractions of 0.5-0.8 wt % and 0.4-0.55 wt % to obtain a printing paste with a high solid content and low shear viscosity; The obtained printing slurry was loaded into a syringe of a direct-write 3D printer and printed on a glass substrate at an air pressure of 16-26 psi; Dry the prints in a constant temperature and humidity chamber to inhibit hydration; The temperature was raised to 700 °C at a rate of 1 °C / min and kept at that temperature for 6 h for degreasing to obtain a standard reference material that matched the matrix of the sample to be tested and had a uniform distribution of doping elements.

2. The method for preparing a solid analytical standard reference material using 3D printing technology according to claim 1, characterized in that: The dispersant is a cationic wetting and dispersing agent or an anionic wetting and dispersing agent.

3. A method for in-situ quantitative analysis of the content of doping elements in solid samples, characterized in that: A series of standard samples with varying doping element contents are prepared using the method for preparing solid analytical standard reference materials using 3D printing technology as described in claim 1 or 2; A quantitative calibration curve is drawn with the actual content of the doping element in the standard sample quantitatively measured by inductively coupled plasma mass spectrometry or inductively coupled plasma atomic emission spectrometry as the abscissa and the response signal of the doping element in the standard sample measured by laser ablation inductively coupled plasma mass spectrometry as the ordinate; Laser ablation inductively coupled plasma mass spectrometry is performed on the sample to be tested, and the content of the doping element in the sample to be tested is analyzed.

4. The method for in-situ quantitative analysis of the content of doping elements in a solid sample according to claim 3, characterized in that: In the in-situ quantitative analysis, the prepared standard sample is used as the external reference material, and the matrix element is used as the internal reference material. After correction of the relative sensitivity factor, the content of the doping element in the sample to be tested is calculated. The calculation formula of the relative sensitivity factor is: RSF = Intensity (i) × Concentration (is) / Intensity (is) × Concentration (i).

5. The method for in-situ quantitative analysis of the content of doping elements in a solid sample according to claim 3, characterized in that: Laser ablation inductively coupled plasma mass spectrometry uses a point scanning or line scanning method to detect the response signal intensity of the doping elements at different positions on the standard sample and the sample to be tested; and / or, The laser ablation adopts a laser wavelength of 213 nm, a laser energy of 40%, a laser ablation aperture of 80 μm and a scanning rate of 70 μm / s.

6. The method for in-situ quantitative analysis of the content of doping elements in a solid sample according to claim 3, characterized in that: In the quantitative calibration curve, the linear relationship between the actual content of the doping element and the response signal intensity is above 0.9996.

7. The method for in-situ quantitative analysis of the content of doping elements in a solid sample according to claim 3, characterized in that: The error between the measured content of the doping elements in the solid samples and the reference values ​​of the corresponding elements obtained by wet digestion is between 0.26% and 9.72%.

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