CN113237841A - Method for detecting content of hydrogen peroxide in etching solution - Google Patents
Method for detecting content of hydrogen peroxide in etching solution Download PDFInfo
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- CN113237841A CN113237841A CN202110569601.4A CN202110569601A CN113237841A CN 113237841 A CN113237841 A CN 113237841A CN 202110569601 A CN202110569601 A CN 202110569601A CN 113237841 A CN113237841 A CN 113237841A
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000005530 etching Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000011550 stock solution Substances 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 37
- 239000003085 diluting agent Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000007865 diluting Methods 0.000 claims abstract description 10
- 238000002798 spectrophotometry method Methods 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- -1 sulfonic acid compound Chemical class 0.000 claims description 12
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- SNKZJIOFVMKAOJ-UHFFFAOYSA-N 3-Aminopropanesulfonate Chemical compound NCCCS(O)(=O)=O SNKZJIOFVMKAOJ-UHFFFAOYSA-N 0.000 claims description 3
- ONZWNZGVZFLMNZ-UHFFFAOYSA-N 1-aminonaphthalene-2-sulfonic acid Chemical compound C1=CC=C2C([NH3+])=C(S([O-])(=O)=O)C=CC2=C1 ONZWNZGVZFLMNZ-UHFFFAOYSA-N 0.000 claims description 2
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- RXCMFQDTWCCLBL-UHFFFAOYSA-N 4-amino-3-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(N)=C(O)C=C(S(O)(=O)=O)C2=C1 RXCMFQDTWCCLBL-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 47
- 238000005259 measurement Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GPFIZJURHXINSQ-UHFFFAOYSA-N acetic acid;nitric acid Chemical compound CC(O)=O.O[N+]([O-])=O GPFIZJURHXINSQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- IOLRIYGJXHZEOF-UHFFFAOYSA-M potassium nitric acid hydroxide Chemical compound [OH-].[K+].O[N+]([O-])=O IOLRIYGJXHZEOF-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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
- G01N1/38—Diluting, dispersing or mixing samples
Abstract
The invention discloses a method for detecting the content of hydrogen peroxide in an etching solution, which comprises the following steps: s1: preparing standard stock solution and stock solution diluent obtained by diluting the standard stock solution by different times; s2: detecting the content of hydrogen peroxide in the standard stock solution and the stock solution diluent diluted by the standard stock solution by different times by using an ultraviolet spectrophotometry to obtain a standard working curve; s3: the volume ratio of the etching solution to be detected to the acidifying reagent is 1: mixing according to the proportion of 0.5-1.5, and uniformly stirring to obtain a mixed solution; s4: diluting the mixed solution with water and standard stock solution in sequence to obtain a to-be-measured diluent; s5: and (4) detecting the hydrogen peroxide content of the diluent to be detected prepared in the step S4 by using an ultraviolet spectrophotometry, and converting the hydrogen peroxide content of the etching solution to be detected according to a standard working curve. The detection method has the advantages of simple operation, short detection time, high measurement precision, small waste liquid amount and the like.
Description
Technical Field
The invention relates to the field of chemical detection, in particular to a method for detecting the content of hydrogen peroxide in an etching solution.
Background
The etching technology can be divided into a wet etching mode and a dry etching mode, wherein the wet etching mode is more widely applied due to the advantages of simple operation, low cost, short time consumption, high reliability, high selectivity and the like. Wet etching is a technique of immersing a material to be etched in an etching solution for corrosion, and a part to be removed is decomposed by using a proper chemical reagent and then converted into a soluble compound to achieve the purpose of removal. From the aspect of market, the current global etching solution production mainly focuses on europe, the united states, the sun, the korean, the china and the like, wherein the europe, the united states and the united states occupy more than 30% of the global market share; japan occupies around 26% of the world; the total proportion of korea plus china reaches 40% and the total proportion reaches 40%. From the upstream and downstream products, the etching solution upstream is chemical raw materials such as phosphoric acid, nitric acid acetic acid, potassium nitrate hydroxide, ammonium hydroxide and the like, and the downstream is industries such as photovoltaic solar energy, semiconductors, flat panel displays and the like. The industry downstream of the etching solution is in a rapid development stage, and the requirement on the etching solution is high, so that the industry development prospect is good.
Most of the conventional etching solutions use hydrogen peroxide as an oxide of an oxidized metal, and the hydrogen peroxide oxidizes the metal and then partially decomposes the metal, followed by conversion into a soluble compound. Hydrogen peroxide is naturally decomposed under alkaline conditions and is not easy to exist stably, while hydrogen peroxide is relatively stable under acidic conditions and can exist stably for a long time. The content of hydrogen peroxide has a crucial influence on the etching effect, so that the content of hydrogen peroxide is very important to detect in the processes of manufacturing, using and the like of the etching solution.
Because of hydrogen peroxide molecules (H)2O2) The reagent contains a peroxy bond (-O-O-), can be used as an oxidizing agent under certain conditions and can also be used as a reducing agent under certain conditions, so the prior determination of hydrogen peroxide mostly adopts a potassium permanganate titration method: KMnO in dilute sulfuric acid medium at room temperature4It can be quantitatively oxidized, and at the end point of titration, the solution is red, and the reaction formula is as follows: 5H2O2+2MnO4-+6H+＝2Mn2++5O2↑+8H2O, the method is relatively simple, but the testing time is long, and the real-time monitoring is not facilitated.
Patent application publication No. CN112321838A mentions that hydrogen peroxide generated by catalytic reaction is detected by an ultraviolet spectrophotometer, and the hydrogen peroxide is measured at 400nm wavelength after reaction for 10min in dark place by using sulfuric acid and titanium potassium oxalate solution. The hydrogen peroxide detected by the method is a main reaction product, has high concentration and small influence factors on detection, and cannot be applied to detection of the content of the hydrogen peroxide in the etching solution (the content of the hydrogen peroxide in the etching solution is usually below 50%, and the detection has many interference factors due to complex formula).
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention aims to provide a method for detecting the content of hydrogen peroxide in an etching solution, which has the advantages of short detection time, convenient operation and high sensitivity.
The technical scheme of the invention is as follows:
in order to achieve the above object, the present invention provides a method for detecting hydrogen peroxide content in an etching solution, comprising the following steps:
s1: preparing standard stock solution and stock solution diluent obtained by diluting the standard stock solution by different times;
s2: detecting the content of hydrogen peroxide by using an ultraviolet spectrophotometry on the standard stock solution prepared in the step S1 and the stock solution diluent diluted by the standard stock solution by different times to obtain a standard working curve;
s3: the volume ratio of the etching solution to be detected to the acidifying reagent is 1: mixing according to the proportion of 0.5-1.5, and uniformly stirring to obtain a mixed solution;
s4: diluting the mixed solution obtained in the step S3 with water and the standard stock solution prepared in the step S1 in sequence to obtain a to-be-measured diluent;
s5: and (4) detecting the hydrogen peroxide content of the diluent to be detected prepared in the step S4 by using an ultraviolet spectrophotometry, and converting the hydrogen peroxide content of the etching solution to be detected according to the standard working curve obtained in the step S2.
It should be noted that, in the sequence of steps of the detection method provided by the present invention, the step S3 may be after the step S2 or before the step S1.
In some embodiments of the invention, in step S3, the acidifying agent is selected from one or more of hydrochloric acid, nitric acid, perchloric acid, hydrofluoric acid, hydrobromic acid, and sulfuric acid, and preferably sulfuric acid with a concentration of 1-9 mol/L.
In some technical schemes of the invention, the pH of the mixed solution obtained in the step S3 is between 2 and 4, preferably between 3 and 4.
In some embodiments of the present invention, the standard stock solution contains hydrogen peroxide, tetramethylammonium hydroxide, titanium sulfate, sulfonic acid compounds, azole compounds, and water.
In some embodiments of the present invention, the standard stock solution contains 5 to 40 wt.% of hydrogen peroxide, 1 to 8 wt.% of tetramethylammonium hydroxide, 1 to 8 wt.% of titanium sulfate, 0.2 to 3 wt.% of sulfonic acid compound, and 0.3 to 1.7 wt.% of azole compound; more preferably, the standard solution contains 5 to 35 wt.% of hydrogen peroxide, 3 to 5 wt.% of tetramethylammonium hydroxide, 2 to 6 wt.% of titanium sulfate, 1 to 2 wt.% of sulfonic acid compound, and 0.8 to 1.3 wt.% of azole compound.
In some embodiments of the present invention, the sulfonic acid compound is selected from one or more of p-toluenesulfonic acid, 2-aminobenzenesulfonic acid, 3-aminopropane sulfonic acid, 4-amino-3-hydroxy-1-naphthalene sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, and sodium m-diaminobenzenesulfonate 5-amino-4-hydroxy-1, 3-benzene disulfonic acid.
In some embodiments of the present invention, the azole compound is selected from one or more of imidazole, pyrazole, triazole, 2-methylimidazole, and 4-methylimidazole.
In some embodiments of the present invention, the standard stock solution and the water used in step S4 are ultrapure water having a resistivity of 18M Ω.
In some technical schemes of the invention, the measurement wavelength of the ultraviolet spectrophotometry is 195-1100 nm, preferably 410-500 nm.
Has the advantages that:
the method for determining the content of the hydrogen peroxide in the etching solution by adopting the ultraviolet spectrophotometry has the advantages of simple operation, short detection time, high measurement precision, small waste liquid amount and the like, and can be widely applied to detection of the content of the hydrogen peroxide in the etching solution.
Drawings
FIG. 1 is a standard working curve of hydrogen peroxide prepared in example 1.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
Example 1
The method for detecting the content of the hydrogen peroxide takes an etching solution which is produced by Jiangsu and Dai electronic technology limited company and has the trade name of CTK2000A as a detection object, wherein the method for detecting the content of the hydrogen peroxide comprises the following steps:
s1: taking a 100mL clean beaker, adding 30g of 30% hydrogen peroxide, 3g of tetramethylammonium hydroxide, 5g of titanium sulfate, 1g of p-toluenesulfonic acid and 1g of triazole, and adding 18M omega of ultrapure water to prepare a standard stock solution with the total mass of 100 g; dividing the standard stock solution into 8 parts, each part being 10g, and diluting 7 parts of the standard stock solution to 2, 4, 6, 8, 10, 20 and 50 times with ultrapure water respectively to obtain stock solution diluents with different concentrations;
s2: placing the standard stock solution prepared in step S1 and the stock solution diluent diluted by different times into a UV1800 UV spectrophotometer of the blessing department, respectively, and adjusting the scanning wavelength to 433nm to obtain a standard working curve, as shown in fig. 1;
s3: mixing the etching solution to be tested with 5mol/L sulfuric acid according to the volume ratio of 1:1, and uniformly stirring to obtain a mixed solution;
s4: diluting the mixed solution obtained in the step S3 by using ultrapure water of 18 MOmega for 100 times, diluting the mixed solution by using the standard stock solution prepared in the step S1 for 10 times, and uniformly mixing to obtain a to-be-measured diluent;
s5: and (4) placing the diluent to be detected obtained in the step S4 in a Youkee UV1800 ultraviolet spectrophotometer, adjusting the scanning wavelength to be 433nm, and converting the content of hydrogen peroxide in the etching solution to be detected according to the standard working curve obtained in the step S2.
The parameters of the ultraviolet spectrophotometer are as follows: wavelength accuracy is +/-2 nm, a slit is 0.1mm hydrogen arc lamp, spectral bandwidth is 4nm, wavelength repeatability is 1nm, luminosity accuracy is +/-0.5% T, stability is +/-0.004A/h, and a 50mm quartz cuvette is adopted.
Comparative example 1
The detection object was the same as in example 1;
the detection method differs from example 1 in that: step S3 is omitted and the other processes are the same.
Example 2
The test object was a mixed solution of the etching solution tested in example 1, which was obtained by etching a copper foil of 0.1mm by 200mm by 100m, manufactured by Feintool, germany, for 30 minutes while stirring (stirring rate 200 r/min);
the detection method was the same as in example 1.
Comparative example 2
The detection object was the same as in example 2;
the detection method differs from example 2 in that: step S3 is omitted and the other processes are the same.
Example 3
The test object was a mixed solution of the etching solution tested in example 1, which was obtained by etching a copper foil of 0.1mm by 200mm by 100m, manufactured by Feintool, germany, for 60 minutes while stirring (stirring rate 200 r/min);
the detection method was the same as in example 1.
Comparative example 3
The detection object was the same as in example 3;
the detection method differs from example 3 in that: step S3 is omitted and the other processes are the same.
Example 4
The test object was a mixed solution of the etching solution tested in example 1, which was obtained by etching a copper foil of 0.1mm by 200mm by 100m, manufactured by Feintool, germany, for 90 minutes while stirring (stirring rate 200 r/min);
the detection method was the same as in example 1.
Comparative example 4
The detection object was the same as in example 4;
the detection method differs from example 4 in that: step S3 is omitted and the other processes are the same.
Example 5
The test object was a mixed solution of the etching solution tested in example 1, which was obtained by etching a copper foil of 0.1mm by 200mm by 100m, manufactured by Feintool, germany, for 120min with stirring (stirring rate of 200 r/min);
the detection method was the same as in example 1.
Comparative example 5
The detection object was the same as in example 5;
the detection method differs from example 5 in that: step S3 is omitted and the other processes are the same.
Example 6
The detection object was the same as in example 1;
the detection method differs from example 1 in that: step S1 is replaced with the following step S1', and the other processes are the same.
S1': taking a 100mL clean beaker, adding 30g of 30% hydrogen peroxide, 5g of tetramethylammonium hydroxide, 2g of titanium sulfate, 2g of 3-aminopropanesulfonic acid and 1.1g of triazole, and then adding 18M omega ultrapure water to prepare a standard stock solution with the total mass of 100 g; dividing the standard stock solution into 8 parts, each of which is 10g, and diluting 7 parts of the standard stock solution to 2, 4, 6, 8, 10, 20 and 50 times with ultrapure water respectively to obtain stock solution diluents with different concentrations.
Comparative example 6
The detection object was the same as in example 1;
the detection method differs from example 6 in that: step S3 is omitted and the other processes are the same.
Example 7
The detection object was the same as in example 2;
the detection method was the same as in example 6.
Comparative example 7
The detection object was the same as in example 2;
the detection method differs from example 7 in that: step S3 is omitted and the other processes are the same.
Example 8
The detection object was the same as in example 3;
the detection method was the same as in example 6.
Comparative example 8
The detection object was the same as in example 3;
the detection method differs from example 8 in that: step S3 is omitted and the other processes are the same.
Example 9
The detection object was the same as in example 4
The detection method was the same as in example 6.
Comparative example 9
The detection object was the same as in example 4;
the detection method differs from example 9 in that: step S3 is omitted and the other processes are the same.
Example 10
The detection object was the same as in example 5;
the detection method was the same as in example 6.
Comparative example 10
The detection object was the same as in example 5;
the detection method differs from example 10 in that: step S3 is omitted and the other processes are the same.
The hydrogen peroxide concentrations tested in the above examples and comparative examples are given in table 1 below:
table 1:
as can be seen from table 1 above, when the etching solution containing hydrogen peroxide of different concentrations is tested, and the etching solution to be tested is not treated by the acidifying reagent, the detection result is significantly higher, and thus, the detection accuracy can be significantly improved in the process of treating the etching solution to be tested by the acidifying reagent.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and equivalent changes and modifications made according to the spirit of the present invention should be covered thereby.
Claims (9)
1. A method for detecting the content of hydrogen peroxide in an etching solution is characterized by comprising the following steps:
s1: preparing standard stock solution and stock solution diluent obtained by diluting the standard stock solution by different times;
s2: detecting the content of hydrogen peroxide by using an ultraviolet spectrophotometry on the standard stock solution prepared in the step S1 and the stock solution diluent diluted by the standard stock solution by different times to obtain a standard working curve;
s3: the volume ratio of the etching solution to be detected to the acidifying reagent is 1: mixing according to the proportion of 0.5-1.5, and uniformly stirring to obtain a mixed solution;
s4: diluting the mixed solution obtained in the step S3 with water and the standard stock solution prepared in the step S1 in sequence to obtain a to-be-measured diluent;
s5: and (4) detecting the hydrogen peroxide content of the diluent to be detected prepared in the step S4 by using an ultraviolet spectrophotometry, and converting the hydrogen peroxide content of the etching solution to be detected according to the standard working curve obtained in the step S2.
2. The method according to claim 1, wherein in step S3, the acidifying reagent is selected from one or more of hydrochloric acid, nitric acid, perchloric acid, hydrofluoric acid, hydrobromic acid, and sulfuric acid.
3. The method as claimed in claim 1, wherein the pH of the mixture obtained in step S3 is between 2-4.
4. The method according to claim 1, wherein the standard stock solution comprises hydrogen peroxide, tetramethylammonium hydroxide, titanium sulfate, sulfonic acid compounds, azole compounds, and water.
5. The method according to claim 4, wherein the standard stock solution contains 10 to 50 wt.% of hydrogen peroxide, 1 to 8 wt.% of tetramethylammonium hydroxide, 1 to 8 wt.% of titanium sulfate, 0.2 to 3 wt.% of sulfonic acid compound, and 0.3 to 1.7 wt.% of azole compound.
6. The method as claimed in claim 4, wherein the sulfonic acid compound is selected from one or more of p-toluenesulfonic acid, 2-aminobenzenesulfonic acid, 3-aminopropane sulfonic acid, 4-amino-3-hydroxy-1-naphthalene sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, and m-diaminobenzene sulfonic acid sodium salt 5-amino-4-hydroxy-1, 3-benzene disulfonic acid.
7. The method for detecting the content of hydrogen peroxide in the etching solution according to claim 4, wherein the azole compound is one or more selected from imidazole, pyrazole, triazole, 2-methylimidazole and 4-methylimidazole.
8. The method as claimed in claim 4, wherein the standard stock solution and the water used in step S4 are ultrapure water having a resistivity of 18M Ω.
9. The method for detecting the content of hydrogen peroxide in the etching solution as claimed in claim 1, wherein the measuring wavelength of the ultraviolet spectrophotometry is 195-1100 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110569601.4A CN113237841B (en) | 2021-05-25 | 2021-05-25 | Method for detecting content of hydrogen peroxide in etching solution |
Applications Claiming Priority (1)
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