CN116773511A - Method for detecting phosphorus content of industrial silicon powder - Google Patents
Method for detecting phosphorus content of industrial silicon powder Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000011574 phosphorus Substances 0.000 title claims abstract description 82
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 82
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000011863 silicon-based powder Substances 0.000 title claims abstract description 39
- 230000003595 spectral effect Effects 0.000 claims abstract description 62
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 51
- 239000010703 silicon Substances 0.000 claims abstract description 51
- 238000003908 quality control method Methods 0.000 claims abstract description 44
- 238000001514 detection method Methods 0.000 claims abstract description 41
- 238000012417 linear regression Methods 0.000 claims abstract description 30
- 239000012488 sample solution Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 72
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 42
- 239000000523 sample Substances 0.000 claims description 33
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims description 22
- 230000029087 digestion Effects 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 11
- 239000002210 silicon-based material Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000010187 selection method Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 22
- 229920005591 polysilicon Polymers 0.000 description 21
- 238000001228 spectrum Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007924 injection Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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Abstract
The invention discloses a method for detecting phosphorus content of industrial silicon powder, which relates to the technical field of industrial silicon powder impurity detection and comprises the following steps: s1, preparing a silicon matrix and acquiring an alternative spectral line; s2, preparing a standard curve solution; s3, preparing a quality control solution; s4, preparing a sample solution to be detected; s5, introducing the standard curve solution in the step S2 and the quality control solution in the step S3 into a spectrometer for detection, selecting an observation mode, and selecting an optimal spectral line of phosphorus from the candidate spectral lines according to the linear regression rate and the deviation of a final detection value relative to the quality control; s6, finally obtaining the accurate content of the phosphorus element in the industrial silicon powder according to the optimal spectral line and the observation mode obtained in the previous steps, namely, the content of the phosphorus element in the industrial silicon powder can be measured by adopting original basic detection equipment, and the problem that the content of the phosphorus element in the industrial silicon powder is difficult to detect in the prior art is solved.
Description
Technical Field
The invention relates to the technical field of industrial silicon powder impurity detection, in particular to a method for detecting phosphorus content of industrial silicon powder.
Background
In recent years, the rapid development of the photovoltaic industry promotes the increase of the yield of polysilicon at home and abroad. The polysilicon is used as a base material of a sustainable new energy source-polysilicon solar cell, and the impurity content in the polysilicon directly influences the photoelectric conversion efficiency of the solar cell, so that the control of the impurity content becomes a key link in the production of the polysilicon. Phosphorus is used as an element in the polysilicon, influences the conductivity of the polysilicon, and the conductivity of the polysilicon is increased and the resistivity is lower along with the increase of the concentration of the phosphorus. Therefore, the method for rapidly and accurately measuring the phosphorus content in the polysilicon is very important for the production and the application of the polysilicon.
Because the phosphorus content in the polysilicon is very low and is in ppb level to ppt level, the existing detection method is that the polysilicon to be measured is drawn into a sample monocrystalline silicon rod, then the resistivity and P/N type of the position which is at least 5 times of the melting area from the head of the sample monocrystalline silicon rod are measured, then a monocrystalline silicon wafer sample with the thickness of about 2mm is cut at the position, and after polishing and cleaning, the phosphorus content of the sample is measured by a low-temperature infrared spectrometer. But the low-temperature infrared spectrometer has the advantages of high equipment price, high failure rate, instability, high sample consumption, high use and maintenance cost and high popularization and use difficulty.
For another example, in a patent application with publication number CN109709203 a, entitled "a method for detecting phosphorus content in polysilicon", mention is made of detecting phosphorus content in polysilicon by inductively coupled plasma mass spectrometry ICP-MS method, comprising the steps of:
(1) Sample treatment: taking 3g of polysilicon sample, digesting with hydrofluoric acid and nitric acid at normal temperature, evaporating acid, and then fixing the volume to 5g with 3% nitric acid;
(2) And (3) starting ICP-MS equipment to enter an ammonia mode for debugging, and directly placing the sample processed in the step (1) into the equipment for testing after the debugging is finished to obtain a result.
The method still has the technical problems mentioned above, and in addition, the problems that the data of detecting the phosphorus element in the industrial silicon powder is not accurate enough by adopting a spectrometer ICP-OES by enterprises, the influence of matrix interference is larger, and the popularization and use difficulty is larger are also existed.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the content of phosphorus element in polysilicon and silicon powder used for preparing polysilicon raw materials is difficult to detect, advanced precision detection equipment is expensive, and popularization and use are inconvenient. In the scheme, the existing ICP-OES spectrometer is still used, and the existing matrix matching method is combined to measure the phosphorus content in the polycrystalline silicon.
The invention is realized by the following technical scheme:
a method for detecting phosphorus content of industrial silicon powder comprises the following steps:
s1, preparing a silicon substrate and obtaining an alternative spectral line: taking Gao Chunjing silicon with the phosphorus content of less than 20ppb in the silicon material, adding hydrofluoric acid and nitric acid for digestion to obtain a silicon substrate solution, adding a phosphorus single standard with known concentration into the silicon substrate solution, performing exposure operation on a spectrometer, and selecting spectral lines with clear points, complete background and concentrated intensity as spectral lines for detecting a sample to be detected by comparing the central point of exposure, the background of an exposure image and the intensity distribution;
s2, preparing standard curve solution:
s201, gao Chunjing silicon with the phosphorus element content of less than 20ppb in the silicon material is taken, and is cooled to room temperature for standby after being digested by adding hydrofluoric acid and nitric acid;
s202, taking phosphorus single standard mother solution, diluting and fixing the volume to obtain standard curve solution with known concentration gradient for later use;
s203, transferring the silicon solution in the step S201 and Gao Chunjing into volumetric flasks with various concentrations in the step S202, and accurately fixing the volume;
s3, preparing a quality control solution: weighing a silicon standard substance, adding hydrofluoric acid and nitric acid for digestion, cooling to room temperature, accurately determining the volume, and taking the silicon standard substance as a quality control solution of the method, wherein the theoretical content of silicon in the quality control solution is known;
s4, preparing a sample solution to be tested:
weighing an industrial silicon powder sample, adding a proper amount of hydrofluoric acid and nitric acid for digestion, cooling to room temperature, and accurately determining the volume to serve as a sample solution to be measured;
s5, introducing the standard curve solution in the step S2 and the quality control solution in the step S3 into a spectrometer for detection, selecting a vertical observation mode, and selecting an optimal spectral line of phosphorus from the candidate spectral lines according to the linear regression rate and the deviation of a final detection value relative to the quality control;
s6, introducing the silicon powder sample solution obtained in the step S4 into a spectrometer for detection on the basis of selecting an optimal spectral line in the step S5, selecting a vertical observation mode, and finally obtaining the accurate content of phosphorus element in the industrial silicon powder through instrument analysis and calculation.
Further, the spectrometer is an ICP-OES spectrometer.
Further, in the step S5, the selection method of the optimal spectral line is as follows: and (3) introducing the standard curve solution in the step (S2) and the sample solution to be detected in the step (S4) into a spectrometer for detection, and comprehensively selecting the optimal spectral line of phosphorus by comparing the linear regression rate, the intensity fluctuation and the final quality control deviation of the silicon standard sample of the spectral line of phosphorus element under different wavelengths.
Further, in the step S5, the priority of the factors of selecting the optimal spectral line is linear regression rate > intensity fluctuation > deviation of quality control of the final silicon standard sample in sequence.
Further, in step S1, 1g of high-purity crystalline silicon is weighed, the content of phosphorus element in Gao Chunjing silicon material is less than 20ppb, hydrofluoric acid and nitric acid are added to digest the material to obtain silicon substrate solution, then 4ppm of single phosphorus standard is added to the silicon substrate solution, exposure operation is performed on a spectrometer, and spectral lines with clear points, complete backgrounds and concentrated intensity are selected as spectral lines for detecting a sample to be detected by comparing the central point of exposure, the background of an exposure image and the intensity distribution.
Further, in the step S2, the method for preparing the standard curve solution includes:
s201a, taking 1g of Gao Chunjing silicon with the phosphorus element content of less than 20ppb in the silicon material, adding a proper amount of hydrofluoric acid and nitric acid for digestion, and cooling to room temperature for later use;
s202a, respectively transferring 50 mu L, 100 mu L and 200 mu L of national standard solution-phosphorus single standard mother solution into a 50mL volumetric flask, and preparing standard curve solutions with single concentration of 1ppm, 2ppm and 4ppm for later use;
and S203a, transferring the Gao Chunjing silicon solution cooled in the step S201a into a 50mL volumetric flask with standard curve solution prepared in the step S202a, and accurately fixing the volume.
Further, in the step S3, the method for preparing the quality control solution includes: 1g of silicon standard substance is weighed, added with hydrofluoric acid and nitric acid for digestion, cooled to room temperature, and the volume is accurately fixed to 50mL, and the silicon standard substance is taken as a quality control solution of the method, wherein the theoretical content of silicon in the quality control solution is 0.0076%.
Further, in the step S4, the preparation method of the sample solution to be tested includes: 1g of industrial silicon powder sample is weighed, added with proper amounts of hydrofluoric acid and nitric acid for digestion, cooled to room temperature, and accurately fixed in volume by 50mL to be used as a sample solution to be measured.
Further, in the step S4, the parallel sample is prepared at the same time when the sample solution to be tested is prepared, so that whether the experimental data have reproducibility can be indirectly verified.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the existing more conventional ICP-OES spectrometer, such as the ICP-OES spectrometer with the model of Prodigy-Xp, is adopted, the influence on phosphorus elements caused by matrix interference is greatly reduced, the data is stable, the content of phosphorus elements in polysilicon can be detected by adopting old equipment or a spectrometer with the functions, and the production cost is reduced without depending on very advanced equipment.
2. According to the invention, exposure treatment is carried out on standard curve solution and sample solution to be detected by using spectral lines recommended by equipment, new spectral lines suitable for detecting phosphorus content are obtained according to specific selection factors, the priority of the selection factors is given, meanwhile, a conventional horizontal observation mode is abandoned, and a vertical observation mode is selected, so that a phosphorus content map is finally obtained, and the map can be used for analyzing and calculating the phosphorus content in an industrial silicon powder sample.
Drawings
FIG. 1 is a graphical representation of the default recommended spectral lines of an ICP-OES spectrometer system database.
FIG. 2 is a linear regression plot of recommended line P213.618 using an ICP-OES spectrometer.
FIG. 3 is an exposure spectrum of the recommended line P213.618 using an ICP-OES spectrometer.
FIG. 4 is a linear regression plot of the recommended line P178.283 using an ICP-OES spectrometer.
FIG. 5 is an exposure spectrum of the recommended line P178.283 using an ICP-OES spectrometer.
FIG. 6 is a linear regression plot of the recommended line P253.561 using an ICP-OES spectrometer.
FIG. 7 is an exposure spectrum of the recommended line P253.561 using an ICP-OES spectrometer.
FIG. 8 is a linear regression plot of recommended line P214.914 using an ICP-OES spectrometer.
FIG. 9 is an exposure spectrum of recommended line P214.914 using an ICP-OES spectrometer.
FIG. 10 is a linear regression plot of line P213.547 using an ICP-OES spectrometer.
FIG. 11 is an exposure spectrum using ICP-OES spectrometer line P213.547.
Fig. 12a and 12b are graphs of detection results of 10 consecutive injections of the quality control solution detected by using spectral lines P213.618, P178.283, P253.561, and P214.91.
Fig. 13 is a graph of detection results of 10 consecutive injections of the quality control solution using line P213.547.
Fig. 14a and 14b are diagrams of detection results of detecting a sample to be detected by using a spectral line P213.547 and continuously sampling a parallel sample 10 times.
FIG. 15 is a regression curve obtained in comparative example 1.
Fig. 16 is an exposure spectrum obtained in comparative example 1.
Fig. 17 is a graph of the detection results of comparative example 1 in which the detection quality control solution was continuously injected 10 times.
Detailed Description
The method for detecting the phosphorus content of the industrial silicon powder provided by the invention is further described by the following examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, since numerous insubstantial modifications and variations of the present invention may be made by those skilled in the art in light of the above teachings, and still fall within the scope of the invention.
In the present invention, the spectrometer ICP-OES is used: prodigy-Xp;
reagent: phosphorus single standard-sodium grinding gram detection technology Co-produced national standard soluble GSBG 6208-90, concentration: 1000. Mu.g/mL.
Silicon standard substance-national standard substance industrial silicon ZBY349 produced by atanan mass-standard science and technology limited company.
Example 1
In this embodiment, the method for detecting the content of phosphorus element in polysilicon by the company is taken as an example, and this scheme is further described.
The content of phosphorus element in raw material silicon powder used for preparing the polysilicon in the industry is about 100ppm, the content is low, and the content of phosphorus element in the polysilicon cannot be detected by adopting a conventional detection method.
A method for detecting phosphorus content of industrial silicon powder comprises the following steps:
the first step: preparation of silicon matrix and acquisition of alternative spectral lines
1g of high-purity crystalline silicon is weighed, the content of phosphorus element in Gao Chunjing silicon material is less than 20ppb, proper amounts of hydrofluoric acid and nitric acid are added for digestion to obtain silicon substrate solution, then 4ppm of phosphorus single standard is added into the silicon substrate solution, the exposure operation is carried out on an ICP-OES spectrometer, spectral lines with clear points, complete backgrounds and concentrated intensity are selected by comparing the central points of exposure, the backgrounds of exposure images and the intensity distribution, and the selected spectral lines are transferred into a detection interface from a database for further selection.
In this embodiment, the content of phosphorus element in the silicon material of the selected substrate is less than 20ppb, and since the experiment itself in this embodiment is configured with a standard curve of phosphorus element, the content of phosphorus element in the silicon substrate is reduced as much as possible, which is more advantageous for the linear regression rate of the standard curve.
The silicon substrate solution added with the phosphorus single standard is placed on a spectrometer for exposure operation, spectral lines recommended by the spectrometer are firstly used, and referring to figure 1, it can be seen that the sensitivity of the system recommended spectral lines P213.618, P178.283, P253.561 and P214.914 is up to 390, the sensitivity is too low, exposure light spots are not obvious, the peak position spectrum intensity is not centralized enough, and the detection result is inaccurate. The sensitivity is generally above 1000, so that the method is suitable for judging whether the element exists or detecting the content of the element. The method comprises the following steps:
referring to fig. 2-9, fig. 2-9 are respectively a linear regression diagram and an exposure spectrogram of the same sample to be detected by adopting a spectrometer recommended observation mode (horizontal observation) according to spectrometer recommended spectral lines P213.618, P178.283, P253.561 and P214.914.
FIG. 2 is a linear regression plot of the recommended line P213.618 using an ICP-OES spectrometer, and FIG. 3 is an exposure plot of line P213.618. As can be seen from fig. 2-3, the default curve spectrogram of the P213.618 system has a linear regression rate of only 0.99827, and the exposure spectrogram has no obvious light spots and concentrated intensity, and is not suitable for judging whether the P element exists or not or detecting the P element content.
FIG. 4 is a linear regression plot of the recommended line P178.283 using an ICP-OES spectrometer, and FIG. 5 is an exposure plot of line P178.283. As can be seen from fig. 4-5, the default curve spectrogram of the P178.283 system has a linear regression rate of only 0.52837, shows anomalies, and has insignificant flare, low intensity, and is not suitable for determining whether the P element exists or detecting the P element content.
FIG. 6 is a linear regression plot of the recommended line P253.561 using an ICP-OES spectrometer and FIG. 7 is an exposure spectrum of line P253.561. As can be seen from fig. 6-7, the default curve spectrogram of the P253.561 system, the linear regression rate 0.99991, shows normal, but the light spot of the exposure spectrogram is not obvious, the intensity is not concentrated enough, and the further verification is needed.
FIG. 8 is a linear regression plot of the recommended line P214.914 using an ICP-OES spectrometer, and FIG. 9 is an exposure spectrum of line P214.914. As can be seen from fig. 6-7, the default curve spectrogram of the P214.914 system, the linear regression rate 0.0908, shows anomalies, and the exposure spectrogram has insignificant light spots and non-concentrated intensity, which is not suitable for judging whether the P element exists or not or detecting the P element content.
In addition, by adopting the new method of the scheme, the spectral line P213.547 is selected, and a vertical observation mode is adopted, and referring to fig. 10 and 11, fig. 10 is a linear regression diagram of the spectral line P213.547, and fig. 11 is an exposure spectrogram of the spectral line P213.547. As can be seen from FIGS. 10-11, the linear regression rate of P213.547 can reach 0.99998, which indirectly proves that the method has good stability, and meanwhile, the exposure spectrogram of the spectral line P213.547 shows clear light spots and concentrated peak position intensity.
Based on the test results, the P253.561 and P213.547 spectral lines are temporarily transferred into a detection interface from a database to serve as spectral lines for detecting samples to be detected, and the system recommended P213.618, P178.283 and P214.914 spectral lines are abandoned after the transfer.
And a second step of: preparing standard curve solution
(1) Weighing Gao Chunjing silicon with phosphorus content less than 20ppb in 1g, adding appropriate amount of hydrofluoric acid and nitric acid for digestion, and cooling to room temperature for standby;
(2) respectively transferring 50 mu L, 100 mu L and 200 mu L of national standard solution-phosphorus single standard (1000 ppm) mother solution into a calibrated 50mL volumetric flask to prepare standard curve solutions with single concentration of 1ppm, 2ppm and 4ppm for later use;
(3) transferring the cooled Gao Chunjing silicon solution in the step (1) into 50mL volumetric flasks for preparing standard curve solutions respectively, and accurately fixing the volume;
in this example, the phosphorus content of the quality control solution is known to be 0.0076%, i.e., 76ppm; the sample weighing amount is 1g, the constant volume is 50ml, the total dilution multiple is 50 times, the single concentration of the solution is 76/50=1.52 ppm, and the solution is just contained in the ranges of 1ppm, 2ppm and 4ppm of the single concentration of the standard curve designed by the scheme, so that the method has more scientificity.
And a third step of: preparing a quality control solution
1g of silicon standard substance is weighed, added with proper amounts of hydrofluoric acid and nitric acid for digestion, cooled to room temperature, and the volume is accurately fixed to 50mL, and the silicon standard substance is taken as a quality control solution in the experiment, wherein the theoretical content of silicon in the quality control solution is 0.0076%. And then, P253.561 and P213.547 spectral lines are respectively adopted to detect the content of phosphorus in the quality control solution so as to further verify whether experimental data have accuracy.
Fig. 12a and 12b are graphs of detection results of 10 consecutive injections of the quality control solution detected by using spectral lines P213.618, P178.283, P253.561, and P214.91. The results of detecting the content of the P element in the quality control solution of the spectral line P253.561 are shown in table 1.
TABLE 1
As can be seen from fig. 12a, 12b and table 1, ten continuous sample injections using the spectral line P253.561 have large fluctuation of detection results, and the actual detection value is far higher than the theoretical value of 0.0076%, i.e. the detection result obtained by using the spectral line P253.561 is unreliable, and is deleted from the spare spectral line.
Fig. 13 is a graph of the detection result of 10 continuous injections of P213.547 detection quality control solution obtained by the scheme of the present invention. The statistical result of the content of the P element in the detection quality control solution of the spectral line P213.547 is shown in table 2.
TABLE 2
As can be seen from FIG. 13 and Table 2, the average value of the above ten samples is 0.0075% (theoretical value of quality control is 0.0076%), which proves that the method is feasible in accuracy, and the fluctuation of 10 samples is small, which proves that the method is feasible in stability.
Fourth step: preparation of a sample solution to be tested
1g of industrial silicon powder sample is weighed, added with proper amounts of hydrofluoric acid and nitric acid for digestion, cooled to room temperature, and accurately fixed in volume of 50mL to serve as a solution to be tested in the experiment, and parallel samples are prepared at the same time when the solution to be tested is prepared so as to further verify whether experimental data have reproducibility.
Fifth step: detecting phosphorus content in a sample to be tested
And (3) introducing the standard curve solution obtained in the second step and the quality control solution obtained in the third step into an ICP-OES (inductively coupled plasma-optical emission spectrometry) of a spectrometer for detection, selecting a vertical observation mode, and selecting an optimal spectral line of phosphorus from the candidate spectral lines according to the linear regression rate and the deviation of a final detection value relative to the quality control.
In the embodiment, the optimal phosphorus spectral line is comprehensively selected by comparing the linear regression rate and the intensity fluctuation of the phosphorus element spectral line under different wavelengths and the deviation of the quality control of the final silicon standard sample. Preferably, the priority of the factors of the selection of the optimal spectral line is in turn the linear regression rate > intensity fluctuation > deviation of the final silicon standard quality control. Combining the operation modes of the first step and the third step to obtain an analysis spectral line with an optimal spectral line P213.547 as a phosphorus element, and selecting a vertical observation as an observation direction to obtain a phosphorus content map.
At present, a batch of industrial silicon powder samples are randomly extracted, a sample solution to be detected is prepared according to the method, and the method is adopted for detection. Referring to fig. 14a and 14b, a graph of detection results obtained by detecting a sample to be detected by using a spectral line P213.547 and continuously sampling the sample in parallel for 10 times is shown in table 3.
TABLE 3 Table 3
As can be seen from fig. 14a, 14b and table 3, parallel samples of industrial silicon powder samples were randomly extracted, and the average value of the two samples was 0.0063%, i.e. the method was directly proved to have high reproducibility, and the detection result obtained by the method was reliable.
Sixth step:
according to the detection result of the fifth step, the phosphorus element content in the industrial silicon powder in the batch is 63ppm.
Comparative example 1
The comparative example still uses the ICP-OES spectrometer with the model of Prodigy-Xp, and the reagent and the industrial silicon powder to be tested all use the same batch of reagents or samples as described above.
The comparative example was prepared by the same method as in example 1 for standard curve solution and quality control solution, and then using P213.547 line, except that horizontal observation was selected as the observation direction to obtain a phosphorus content profile of the quality control solution. FIG. 15 is a linear regression diagram of a quality control solution under this method; fig. 16 is an exposure spectrum of line P213.547 under this method.
Fig. 17 is a graph of the detection results of 10 consecutive injections of the control solution in line P213.547 using the comparative example scheme, where column 4 shows the concentration in units of: ppm, conversion formula: 1% = 10 4 ppm. The statistical result of the content of the P element in the detection quality control solution of the spectral line P213.547 is shown in table 4.
TABLE 4 Table 4
As can be seen from fig. 15, 16, 17 and table 4, the linear regression rate of the curve obtained by this method was 0.9996007, which is inferior to the linear regression rate obtained by the vertical observation; and the exposure spectrogram still has obvious interference; the average value of the results obtained when the final detection standard sample is observed horizontally is 0.0066 percent, which is different from the theoretical value of 0.0076 percent, and the method is not suitable for accurately detecting the phosphorus content in the industrial silicon powder.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation, etc. of the above embodiment according to the technical matter of the present invention fall within the scope of the present invention.
Claims (9)
1. The method for detecting the phosphorus content of the industrial silicon powder is characterized by comprising the following steps of:
s1, preparing a silicon substrate and obtaining an alternative spectral line: taking Gao Chunjing silicon with the phosphorus content of less than 20ppb in the silicon material, adding hydrofluoric acid and nitric acid for digestion to obtain a silicon substrate solution, adding a phosphorus single standard with known concentration into the silicon substrate solution, performing exposure operation on a spectrometer, and selecting spectral lines with clear points, complete background and concentrated intensity as spectral lines for detecting a sample to be detected by comparing the central point of exposure, the background of an exposure image and the intensity distribution;
s2, preparing standard curve solution:
s201, gao Chunjing silicon with the phosphorus element content of less than 20ppb in the silicon material is taken, and is cooled to room temperature for standby after being digested by adding hydrofluoric acid and nitric acid;
s202, taking phosphorus single standard mother solution, diluting and fixing the volume to obtain standard curve solution with known concentration gradient for later use;
s203, transferring the silicon solution in the step S201 and Gao Chunjing into volumetric flasks with various concentrations in the step S202, and accurately fixing the volume;
s3, preparing a quality control solution: weighing a silicon standard substance, adding hydrofluoric acid and nitric acid for digestion, cooling to room temperature, accurately determining the volume, and taking the silicon standard substance as a quality control solution of the method, wherein the theoretical content of silicon in the quality control solution is known;
s4, preparing a sample solution to be tested:
weighing an industrial silicon powder sample, adding a proper amount of hydrofluoric acid and nitric acid for digestion, cooling to room temperature, and accurately determining the volume to serve as a sample solution to be measured;
s5, introducing the standard curve solution in the step S2 and the quality control solution in the step S3 into a spectrometer for detection, selecting a vertical observation mode, and selecting an optimal spectral line of phosphorus from the candidate spectral lines according to the linear regression rate and the deviation of a final detection value relative to the quality control;
s6, introducing the silicon powder sample solution obtained in the step S4 into a spectrometer for detection on the basis of selecting an optimal spectral line in the step S5, selecting a vertical observation mode, and finally obtaining the accurate content of phosphorus element in the industrial silicon powder through instrument analysis and calculation.
2. The method for detecting the phosphorus content of the industrial silicon powder according to claim 1, wherein the method comprises the following steps: the spectrometer is an ICP-OES spectrometer.
3. The method for detecting phosphorus content of industrial silicon powder according to claim 1, wherein in the step S5, the selection method of the optimal spectral line is as follows: and (3) introducing the standard curve solution in the step (S2) and the sample solution to be detected in the step (S4) into a spectrometer for detection, and comprehensively selecting the optimal spectral line of phosphorus by comparing the linear regression rate, the intensity fluctuation and the final quality control deviation of the silicon standard sample of the spectral line of phosphorus element under different wavelengths.
4. A method for detecting phosphorus content of industrial silicon powder according to claim 3, wherein in step S5, the priority of the factors of the selection of the optimal spectral line is linear regression rate > intensity fluctuation > deviation of final silicon standard sample quality control in turn.
5. The method for detecting the phosphorus content of the industrial silicon powder according to claim 1, wherein the method comprises the following steps:
in the step S1, 1g of high-purity crystalline silicon is weighed, the content of phosphorus element in Gao Chunjing silicon material is less than 20ppb, hydrofluoric acid and nitric acid are added for digestion to obtain silicon substrate solution, then 4ppm of phosphorus single standard is added into the silicon substrate solution, exposure operation is carried out on a spectrometer, and spectral lines with clear points, complete backgrounds and concentrated intensity are selected as spectral lines for detecting a sample to be detected by comparing the central point of exposure, the background of an exposure image and the intensity distribution.
6. A method for detecting phosphorus content in industrial silicon powder as defined in claim 5, wherein the method for preparing standard curve solution in step S2 comprises the following steps:
s201a, taking 1g of Gao Chunjing silicon with the phosphorus element content of less than 20ppb in the silicon material, adding a proper amount of hydrofluoric acid and nitric acid for digestion, and cooling to room temperature for later use;
s202a, respectively transferring 50 mu L, 100 mu L and 200 mu L of national standard solution-phosphorus single standard mother solution into a 50mL volumetric flask, and preparing standard curve solutions with single concentration of 1ppm, 2ppm and 4ppm for later use;
and S203a, transferring the Gao Chunjing silicon solution cooled in the step S201a into a 50mL volumetric flask with standard curve solution prepared in the step S202a, and accurately fixing the volume.
7. A method for detecting phosphorus content in industrial silicon powder as defined in claim 6, wherein in step S3, the method for preparing the quality control solution comprises the following steps: 1g of silicon standard substance is weighed, added with hydrofluoric acid and nitric acid for digestion, cooled to room temperature, and the volume is accurately fixed to 50mL, and the silicon standard substance is taken as a quality control solution of the method, wherein the theoretical content of silicon in the quality control solution is 0.0076%.
8. A method for detecting phosphorus content in industrial silicon powder as defined in claim 7, wherein in step S4, the preparation method of the sample solution to be detected is as follows: 1g of industrial silicon powder sample is weighed, added with proper amounts of hydrofluoric acid and nitric acid for digestion, cooled to room temperature, and accurately fixed in volume by 50mL to be used as a sample solution to be measured.
9. A method for detecting phosphorus content in industrial silicon powder as defined in claim 8, wherein in step S4, parallel samples are prepared at the same time when preparing the sample solution to be detected.
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