CN113933376A - Semiconductor solvent ICP-MS determination method based on multiple dilution method - Google Patents
Semiconductor solvent ICP-MS determination method based on multiple dilution method Download PDFInfo
- Publication number
- CN113933376A CN113933376A CN202111257769.8A CN202111257769A CN113933376A CN 113933376 A CN113933376 A CN 113933376A CN 202111257769 A CN202111257769 A CN 202111257769A CN 113933376 A CN113933376 A CN 113933376A
- Authority
- CN
- China
- Prior art keywords
- diluted sample
- solvent
- semiconductor
- sample
- icp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 38
- 239000002904 solvent Substances 0.000 title claims abstract description 29
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000003113 dilution method Methods 0.000 title claims abstract description 15
- 239000012470 diluted sample Substances 0.000 claims abstract description 44
- 239000012895 dilution Substances 0.000 claims abstract description 41
- 238000010790 dilution Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 14
- 239000006184 cosolvent Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 238000007865 diluting Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012086 standard solution Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims 2
- 239000000523 sample Substances 0.000 abstract description 28
- 238000005259 measurement Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 11
- 239000011573 trace mineral Substances 0.000 abstract description 2
- 235000013619 trace mineral Nutrition 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 229920002120 photoresistant polymer Polymers 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012487 rinsing solution Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 206010000117 Abnormal behaviour Diseases 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical class O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
Abstract
The invention provides a semiconductor chemical ICP-MS measuring method based on a multiple dilution method, which comprises the following steps: firstly, adding a cosolvent solvent into a semiconductor solvent to be measured, which cannot be mixed with water, to form a mixed organic solvent; then adding pure water into the mixed organic solvent for dilution to obtain a No. 1 diluted sample; adding pure water into the 1# diluted sample for dilution to obtain a 2# diluted sample; diluting a sample by using a No. 1 sample for one element in a semiconductor solvent to be measured, scanning by using an inductively coupled plasma mass spectrometer to obtain a standard curve, and calculating the concentration C1 of the No. 1 diluted sample; the concentration C2 of the element in the 2# diluted sample is calculated in the same way; and substituting the result into a fitting algorithm formula to obtain the concentration of the element in the semiconductor solvent to be measured. The invention carries out background fitting operation on the signal value measured by the ICP-MS of the mixed matrix by different dilution multiple methods of the same sample, thereby realizing accurate measurement of trace elements.
Description
Technical Field
The invention relates to the technical field of trace element control of wet electronic chemicals, in particular to a semiconductor solvent ICP-MS (inductively coupled plasma-mass spectrometry) determination method based on a multiple dilution method.
Background
The downstream industrial chain of wet electronic chemicals is mostly the technology-intensive industries such as semiconductor manufacturing, display panels, solar photovoltaic cells and lithium ion battery manufacturing, and has different requirements on the purity and cleanliness of products according to different application fields; in the wafer manufacturing process, wet electronic chemicals are mainly used to clean contaminants such as particles, organic residues, metal ions, native oxide layers, and the like. In the etching process, the etching solution and a specific film material are subjected to chemical reaction, so that the film in the uncovered area of the photoresist is removed, the pattern transfer is realized, and the structure of the device is obtained. The wet electronic chemicals are also applied to the process links of cleaning, sputtering, yellow light, and the like in the field of back-end high-end packaging. The semiconductor has strict requirements on the content of trace metal impurities, the particle size and the number of particles, the content of anionic impurities and the like of wet electronic chemicals. Therefore, according to the Semiconductor Equipment and Materials International (SEMI) standard, wet electronic chemicals applied in the semiconductor field are concentrated at SEMI G3, G4 level, and the narrower the integrated circuit line width, the higher the required standard. The detection of trace impurity elements is a key technology of quality control, and is mostly realized by accurate quantification of an inductively coupled plasma spectrometer (ICP-OES for short) and an inductively coupled plasma mass spectrometer (ICP-MS for short).
In the detection of ICP-OES, ICP-MS and the like, diluent interference is a long-standing problem, the essence of the problem is that the diluent cannot avoid substances with spectral or mass spectrum response, the content of introduced impurities is usually very high, particularly in the analysis of ppt semiconductor metal impurities, the phenomenon of peculiar 'solvent effect' or 'matrix effect' is easy to generate, the reverse logic of a detection result and a dilution multiple is caused, and the best mode for solving the problem is to adopt a mobile phase with an initial proportion as the diluent. "matrix effect" broadly refers to the condition where certain components of a sample are present in a different state in a diluent than in the sample, resulting in abnormal behavior during the test. In the development of the analysis method, the mobile phase is taken as a diluent, and if the problems of solubility, solution stability and the like are met, a cosolvent, a stabilizing agent and the like can be properly added into the diluent.
Some common semiconductor materials are listed below
1. Wet electronic chemical detection of species
(1) Acid and alkali: high-purity hydrochloric acid, high-purity sulfuric acid, high-purity nitric acid, high-purity hydrofluoric acid, high-purity glacial acetic acid, high-purity oxalic acid, electronic grade pure water, electronic grade hydrogen peroxide, a potassium hydroxide solution, a sodium hydroxide solution and electronic grade phosphoric acid;
(2) etching: aluminum etching solution, nickel silver etching solution, silicon etching solution, gold etching solution, copper etching solution, developing solution, stripping solution, cleaning solution, ITO etching solution, slow release agent and BOE;
(3) solvents: methanol, ethanol, isopropanol, acetone, tetramethylammonium hydroxide (TMAH), toluene, xylene, trichloroethylene, cyclohexane, N-methylpyrrolidone, propylene glycol monomethyl ether acetate, and the like;
2. detection type of photoresist and matched reagent
Photoresist, negative photoresist developing solution, negative photoresist rinsing solution, negative photoresist developing rinsing solution, positive photoresist developing solution, positive photoresist diluent, edge photoresist cleaning agent, negative photoresist stripping solution, positive photoresist stripping solution and the like;
it can be seen that, when various samples are injected by ICP-MS (inductively coupled plasma mass spectrometer), the influence on the state of the plasma is various; another important reason for the reverse logic of the detection result and the dilution factor is that in the process of testing ppt-level impurities of an ultra-clean semiconductor solvent by using an ICP-MS (inductively coupled plasma mass spectrometer), a large amount of hydrocarbon samples are not allowed to be introduced, the selectable diluent is ultrapure water, and the addition of pure water can cause the change of organic and inorganic properties of the samples, finally cause the properties of the samples, the samples with different dilution factors and the samples diluted by adding a standard to be inconsistent, and mainly show the influence on the plasma flame state, under the condition, the standard curve is not suitable for the quantitative analysis of the samples with different dilution factors; in addition, due to the different properties of the test samples, the data measured by adding the standard to the background diluent are not suitable for the background subtraction operation of the sample added with the organic solvent.
Disclosure of Invention
In order to overcome the defects that in the existing operation process, due to the fact that various conditions such as different properties, different hydrocarbon compositions, dilution of a sample by acid, dilution of the sample by water and the like are input, the state change of plasma is caused, the interference and disorder of a signal value are further influenced, and finally the reverse logic of a rogue detection result and a dilution multiple appears, the invention provides a semiconductor solvent ICP-MS determination method based on a multiple dilution method.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the semiconductor solvent ICP-MS determination method based on the multiple dilution method comprises the following steps:
(1) adding a cosolvent with the mass of 5-50% of the semiconductor solvent to be measured, which cannot be mixed with water, into the semiconductor solvent to be measured to form a mixed organic solvent;
(2) diluting the mixed organic solvent obtained in the step (1) with pure water to obtain a 1# diluted sample, wherein the mass ratio of the mixed organic solvent to the pure water in the 1# diluted sample is D1, and D1 is less than 2: 8;
(3) adding pure water into the 1# diluted sample for dilution to obtain a 2# diluted sample, wherein the mass ratio of the 1# diluted sample to the pure water in the 2# diluted sample is D2, D2 is less than 2:8, and D2 is not equal to D1;
(4) scanning an element in the semiconductor solvent to be measured by using the No. 1 diluted sample obtained in the step (2) by using an inductively coupled plasma mass spectrometer, adding an acidic standard solution with the mass ratio of 1-5% after the 1# diluted sample is scanned once, and then scanning the next time; by analogy, scanning for more than three times to obtain a standard curve; calculating the concentration C1 of the 1# diluted sample according to the standard curve and the signal value obtained by scanning;
(5) scanning the 2# diluted sample obtained in the step (3) by using an inductively coupled plasma mass spectrometer by using the method in the step (4) and calculating the concentration C2 of the element in the 2# diluted sample;
(6) and substituting the result into a fitting algorithm formula to obtain the concentration C of the element in the semiconductor solvent to be measured, wherein the fitting algorithm formula is as follows:
further, the cosolvent in the step (1) is one or a combination of methanol, ethanol, methyl ether, acetone, ethyl acetate and N-methyl pyrrolidone.
Further, the impurity content of pure water used in the step (2) and/or the step (3) is as low as 1ppb as possible.
Further, the acidic standard solution used in the step (4) and/or the step (5) is a chromatographic pure nitric acid matrix.
The invention has the beneficial effects that:
1. the invention cross-confirms and verifies the test result by a multiple dilution method, thereby avoiding the contingency of the measurement result of trace impurities of the semiconductor grade solvent.
2. The invention can lead the calculation confirmation result to be infinitely close to the true value through the cross confirmation and verification test result of the multiple dilution method.
3. The invention uses the multiple dilution of the sample, and the measured results are substituted into the fitting algorithm formula deduced by the invention; measurement interference caused by plasma flame change in an inductively coupled plasma mass spectrometer (ICP-MS) is eliminated.
4. The invention can fundamentally solve the problem of logic confusion of sample measurement results due to different dilution times and has originality.
5. The semiconductor nano process supporting Moore's law puts forward the requirement of extreme control on the used chemical impurities, and under the trend, the invention breaks through the bottleneck of detection accuracy and opens a new window for meeting the harsh requirement of the semiconductor chemical detection technology.
Detailed Description
The process of the present invention is illustrated below with reference to specific examples, which include, but are not limited to, the following examples.
Example 1:
the semiconductor solvent ICP-MS determination method based on the multiple dilution method comprises the following specific steps:
step (1): inspecting semiconductor-grade pure water equipment to ensure that the impurity content of pure water is lower than 1 ppb;
step (2): taking an electronic grade azomethylpyrrolidone sample as an example, the operation that the sample is not miscible with water is ignored because the semiconductor solvent can be miscible with water and the miscibility test is confirmed by a visual method;
and (3): the dilution ratio of the azomethylpyrrolidone to water is less than 2:8 by mass, and the record is that D1 is 0.2; similarly, selecting a dilution ratio which is less than 2:8 in terms of mass ratio and is different from that of the first time, and repeating the operation, wherein D2 is recorded as 0.1;
and (4): taking calcium element in nitrogen methyl pyrrolidone as an example, diluting the sample obtained in the step (1) and the step (2), using an inductively coupled plasma mass spectrometer (ICP-MS), sequentially adding an acid standard solution with the mass ratio of 1% -5% after the sample is scanned once, wherein the acid standard solution is a chromatographic pure nitric acid matrix and is used for next scanning, and the adding times are not less than three times to obtain a standard curve which can be confirmed; and calculating corresponding concentration values by using a standard curve according to the signal values obtained by labeling and scanning for several times, wherein the concentration value obtained by the first dilution measurement is C1-32 ppb, the concentration value obtained by the second dilution measurement is C2-20 ppb, and the like.
And (5): substituting the sample results with different dilution times into a fitting algorithm formula:
wherein: dilution factor of D1-1# diluted sample
Dilution factor of D2-2# diluted sample
Concentration results for C1-1# diluted samples
Concentration results for C2-2# diluted samples
Final calculation of calcium element in C-N-methyl pyrrolidone
Example 2:
the semiconductor solvent ICP-MS determination method based on the multiple dilution method comprises the following specific steps:
step (1): inspecting semiconductor-grade pure water equipment to ensure that the impurity content of pure water is lower than 1 ppb;
step (2): taking a benzene sample as an example, the miscibility test visually confirms that the diluted semiconductor organic solvent is not miscible with water;
and (3): mixing the sample benzene and cosolvent ethanol in a ratio of 1: 9 to form a mixed organic solvent, becomes a thermodynamically stable system, is transparent and clear in appearance, and finally can be diluted and dispersed in water in the subsequent step by micro nano liquid drops.
And (4): the dilution ratio of the mixed organic solvent obtained in the step (3) to water is less than 2:8 by mass, and is recorded as D1 ═ 0.2; similarly, selecting a dilution ratio which is less than 2:8 in terms of mass ratio and is different from that of the first time, repeating the operation, and recording the D2 as 0.05;
and (5): taking sodium element in a sample as an example, diluting the sample obtained in the step (1) and the step (2), using an inductively coupled plasma mass spectrometer (ICP-MS), after scanning the sample once, sequentially adding 1-5% of acid standard liquid by mass ratio, wherein the acid standard liquid is a chromatographic pure nitric acid matrix and is used for the next scanning, and the adding times are not less than three times to obtain a standard curve which can be confirmed; and calculating corresponding concentration values by using a standard curve according to the signal values obtained by labeling and scanning for several times, wherein the concentration value obtained by the first dilution measurement is C1-160 ppb, the concentration value obtained by the second dilution measurement is C2-220 ppb, and the like.
And (6): substituting the sample results with different dilution times into a fitting algorithm formula:
wherein: dilution factor of D1-1# diluted sample
Dilution factor of D2-2# diluted sample
Concentration results for C1-1# diluted samples
Concentration results for C2-2# diluted samples
C-final calculation of the sodium concentration in the benzene sample
Example 3:
the semiconductor solvent ICP-MS determination method based on the multiple dilution method comprises the following specific steps:
step (1): inspecting semiconductor-grade pure water equipment to ensure that the impurity content of pure water is lower than 1 ppb;
step (2): taking a semiconductor grade cyclopentanone sample as an example, the miscibility test is carried out by a visual inspection method to confirm that the diluted semiconductor organic solvent is not miscible with water;
and (3): mixing cyclopentanone with cosolvent ethanol, acetone and diethyl ether in a ratio of 2: 4: 2: 2 to form a mixed organic solvent, becoming a thermodynamically stable system, being transparent and clear in appearance, and finally diluting and dispersing the cyclopentanone in water of the subsequent step by using tiny nano-droplets.
And (4): the dilution ratio of the mixed organic solvent obtained in step (3) to water is close to 2:8 by mass, and is recorded as D1 ═ 0.35; similarly, a dilution ratio close to 2:8 by mass and different from the first time is selected, and the operation is repeated, and the record is that D2 is 0.15;
and (5): taking iron element in a sample as an example, taking the diluted sample obtained in the step (1) and the step (2), using an inductively coupled plasma mass spectrometer (ICP-MS), after scanning the sample once, sequentially adding 0.5ppb, 2ppb, 10ppb and 20ppb of standard solution of nitric acid with the mass ratio of 1.5%, wherein the acidic standard solution is a chromatographic pure nitric acid matrix and is used for the next scanning and is labeled for four times to obtain a qualified standard curve; calculating corresponding concentration values by using a standard curve according to signal values obtained by labeling and scanning for several times, wherein the concentration value obtained by the first dilution measurement is C1-9 ppb, the concentration value obtained by the second dilution measurement is C2-5 ppb, and the like; the dilution ratio of the mixed organic solvent obtained in step (3) to water is close to 2:8 by mass, and is recorded as D3 ═ 0.3; similarly, a dilution ratio close to 2:8 in mass ratio and different from the first time is selected, and the operation is repeated, and the record is that D4 is 0.2; the concentration value obtained by the first dilution measurement was 8ppb to C3, and the concentration value obtained by the second dilution measurement was 6ppb to C4.
And (6): substituting the sample results with different dilution times into a fitting algorithm formula:
wherein: dilution factor of D1-1# diluted sample,
dilution factor of D2-2# diluted sample,
concentration results for C1-1# diluted samples,
concentration results for C2-2# diluted samples,
c-final calculation of the concentration of iron element in the cyclopentanone sample.
Wherein: dilution factor of D3-1# diluted sample,
dilution factor of D4-2# diluted sample,
concentration results for C3-1# diluted samples,
concentration results for C4-2# diluted samples,
c2 — final calculation of iron element concentration in this cyclopentanone sample.
The results obtained twice are relatively close, and the results of multiple times of respective measurement are substituted into a fitting algorithm formula deduced by the invention; measurement interference caused by plasma flame change in an inductively coupled plasma mass spectrometer (ICP-MS) is eliminated.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (4)
1. A semiconductor solvent ICP-MS measuring method based on a multiple dilution method is characterized by comprising the following steps:
(1) adding a cosolvent with the mass of 5-50% of the semiconductor solvent to be measured, which cannot be mixed with water, into the semiconductor solvent to be measured to form a mixed organic solvent;
(2) diluting the mixed organic solvent obtained in the step (1) with pure water to obtain a 1# diluted sample, wherein the mass ratio of the mixed organic solvent to the pure water in the 1# diluted sample is D1, and D1 is less than 2: 8;
(3) adding pure water into the 1# diluted sample for dilution to obtain a 2# diluted sample, wherein the mass ratio of the 1# diluted sample to the pure water in the 2# diluted sample is D2, D2 is less than 2:8, and D2 is not equal to D1;
(4) scanning an element in the semiconductor solvent to be measured by using the No. 1 diluted sample obtained in the step (2) by using an inductively coupled plasma mass spectrometer, adding an acidic standard solution with the mass ratio of 1-5% after the 1# diluted sample is scanned once, and then scanning the next time; by analogy, scanning for more than three times to obtain a standard curve; calculating the concentration C1 of the 1# diluted sample according to the standard curve and the signal value obtained by scanning;
(5) scanning the 2# diluted sample obtained in the step (3) by using an inductively coupled plasma mass spectrometer by using the method in the step (4) and calculating the concentration C2 of the element in the 2# diluted sample;
(6) and substituting the result into a fitting algorithm formula to obtain the concentration C of the element in the semiconductor solvent to be measured, wherein the fitting algorithm formula is as follows:
2. the multiple dilution method-based semiconductor solvent ICP-MS measurement method according to claim 1, wherein the cosolvent in the step (1) is one or more of methanol, ethanol, methyl ether, acetone, ethyl acetate and N-methylpyrrolidone.
3. The multiple dilution method-based semiconductor solvent ICP-MS measuring method according to claim 1, characterized in that the pure water used in step (2) and/or step (3) has an impurity content of less than 1ppb as low as possible.
4. The multiple dilution method-based semiconductor solvent ICP-MS measurement method according to claim 1, wherein the acidic standard solution used in the step (4) and/or the step (5) is a chromatographically pure nitric acid matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111257769.8A CN113933376A (en) | 2021-10-27 | 2021-10-27 | Semiconductor solvent ICP-MS determination method based on multiple dilution method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111257769.8A CN113933376A (en) | 2021-10-27 | 2021-10-27 | Semiconductor solvent ICP-MS determination method based on multiple dilution method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113933376A true CN113933376A (en) | 2022-01-14 |
Family
ID=79284542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111257769.8A Pending CN113933376A (en) | 2021-10-27 | 2021-10-27 | Semiconductor solvent ICP-MS determination method based on multiple dilution method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113933376A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01124951A (en) * | 1987-06-29 | 1989-05-17 | Yokogawa Electric Corp | High frequency inductively coupled plasma mass spectrograph |
| US20150348768A1 (en) * | 2012-12-26 | 2015-12-03 | Korea Research Institute Of Standards And Science | Combustion pretreatment-isotope dilution mass spectrometry |
| CN105675709A (en) * | 2016-02-19 | 2016-06-15 | 金川集团股份有限公司 | Method for rapidly measuring trace osmium with inductively coupled plasma-massspectrometry |
| CN109738381A (en) * | 2018-08-01 | 2019-05-10 | 刘茂诚 | Minimal feeding device and its detection method |
| CN111060582A (en) * | 2019-12-17 | 2020-04-24 | 上海微谱化工技术服务有限公司 | Qualitative and quantitative analysis and detection method for trace elements in cosmetics |
| KR20210078882A (en) * | 2019-12-19 | 2021-06-29 | 중앙대학교 산학협력단 | Multi-elemental analysis of blood by inductively coupled plasma/mass spectrometry |
| CN113504291A (en) * | 2021-06-16 | 2021-10-15 | 宁波锦越新材料有限公司 | Sample preparation method and detection method for determining impurities in ultra-high-purity aluminum by utilizing ICP-MS (inductively coupled plasma-mass spectrometry) |
-
2021
- 2021-10-27 CN CN202111257769.8A patent/CN113933376A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01124951A (en) * | 1987-06-29 | 1989-05-17 | Yokogawa Electric Corp | High frequency inductively coupled plasma mass spectrograph |
| US20150348768A1 (en) * | 2012-12-26 | 2015-12-03 | Korea Research Institute Of Standards And Science | Combustion pretreatment-isotope dilution mass spectrometry |
| CN105675709A (en) * | 2016-02-19 | 2016-06-15 | 金川集团股份有限公司 | Method for rapidly measuring trace osmium with inductively coupled plasma-massspectrometry |
| CN109738381A (en) * | 2018-08-01 | 2019-05-10 | 刘茂诚 | Minimal feeding device and its detection method |
| CN111060582A (en) * | 2019-12-17 | 2020-04-24 | 上海微谱化工技术服务有限公司 | Qualitative and quantitative analysis and detection method for trace elements in cosmetics |
| KR20210078882A (en) * | 2019-12-19 | 2021-06-29 | 중앙대학교 산학협력단 | Multi-elemental analysis of blood by inductively coupled plasma/mass spectrometry |
| CN113504291A (en) * | 2021-06-16 | 2021-10-15 | 宁波锦越新材料有限公司 | Sample preparation method and detection method for determining impurities in ultra-high-purity aluminum by utilizing ICP-MS (inductively coupled plasma-mass spectrometry) |
Non-Patent Citations (1)
| Title |
|---|
| 何蔓, 胡斌, 江祖成: "用于研究ICP-MS中基体效应的逐级稀释法", 高等学校化学学报, no. 12, 15 December 2004 (2004-12-15), pages 2232 - 2235 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8114825B2 (en) | Photoresist stripping solution | |
| KR101242246B1 (en) | Apparatus for measuring impurities on wafer and Method for measuring impurities on wafer | |
| CN107389663A (en) | A kind of method for detecting metal ion content in silicon chip surface oxide-film | |
| CN100373537C (en) | Evaluation method for chemical solution, qualification method for chemical solution and method for manufacturing semiconductor device | |
| CN103091277A (en) | Method for detecting organic contamination on surface of large-sized monocrystalline silicon wafer by infrared transmission | |
| CN113933376A (en) | Semiconductor solvent ICP-MS determination method based on multiple dilution method | |
| TWI781561B (en) | Method for measuring superficial metal content of a wafer | |
| Beebe et al. | Monitoring wafer cleanliness and metal contamination via VPD ICP-MS: Case studies for next generation requirements | |
| CN108919617A (en) | A kind of TFT-LCD negativity developer solution | |
| CN105158323A (en) | Detection method for metallic element in liquid crystal material | |
| Horn | Applications of ICP-MS in semiconductor industry | |
| JP2014130917A (en) | Component concentration measuring method of etching solution and management method of etching solution | |
| TW202141565A (en) | Automated system for online detection of organic molecular impurities in semiconductor grade chemicals | |
| US6146909A (en) | Detecting trace levels of copper | |
| JP5541190B2 (en) | Metal impurity concentration evaluation method for P-type silicon wafer | |
| US7622305B2 (en) | Multiple acid solution characterization | |
| Ko et al. | Evaluation of metal migration and determination of trace metals after microwave digestion for lithographic materials | |
| Chen et al. | Study for cross contamination between cmos image sensor and ic product | |
| Chang et al. | Coupling of an electrodialyzer with inductively coupled plasma mass spectrometry for the on-line determination of trace impurities in silicon wafers after surface metal extraction | |
| CN115793416B (en) | Method for manufacturing semiconductor device and method for monitoring impurities of photolithography process chemicals | |
| CN115452772B (en) | Detection method of adsorbate on surface of LCD screen | |
| Su et al. | The Monitor and Management of Sulfide Contamination for Probing FAB clean room | |
| WO2024001016A1 (en) | Enrichment method and analysis method for precious metal elements on surface of wafer | |
| Song et al. | The inspection solutions and reduction of extreme tiny poly residue | |
| JPH1197321A (en) | Method for identifying contamination source |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |