CN114740070A - Method for detecting concentration of copper ions in acidic copper plating solution - Google Patents
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- 239000010949 copper Substances 0.000 title claims abstract description 64
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 54
- 238000007747 plating Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 21
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 27
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 238000012360 testing method Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- -1 silver ions Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- 239000007772 electrode material Substances 0.000 claims 1
- 229910001432 tin ion Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000004445 quantitative analysis Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Pathology (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention provides a method for detecting the concentration of copper ions in an acidic copper plating solution, which adopts an electrochemical three-electrode test system (an embedded microelectrode is taken as a working electrode) and combines a cyclic voltammetry for determination. The embedded microelectrode avoids the defect that the traditional microdisk electrode can not be completely dissolved out due to copper overflow on the surface of the microelectrode caused by repeated deposition and dissolution in copper plating solution. The embedded microelectrode can avoid the problem that copper can not be completely dissolved out. The deposition peak and the dissolution peak of the cyclic voltammetry are utilized to carry out quantitative analysis and detection on copper ions in the acidic copper plating solution, and the method is rapid and accurate.
Description
Technical Field
The invention relates to an analysis and determination method of inorganic ions, in particular to an electrochemical analysis method of copper ions, and specifically relates to a method for determining the concentration of copper ions in an acidic copper plating solution by using an embedded microelectrode.
Background
The stability of the copper electroplating is high, the application range of the working temperature and the solution concentration is wide, the copper layer is compact, the bonding force is excellent, the operation is simple, and the copper electroplating solution is widely applied to various industries, such as: the copper plating process is suitable for all metal and nonmetal surfaces. Copper sulfate is generally used as the main salt of electrolytic copper. The sulfate copper plating is a plating solution system which is most widely applied in the current industrial production and has the advantages of simple process, high deposition speed, low cost and the like. The copper ion content in the acidic copper plating solution is an important parameter of the copper plating process. The copper ions in the acidic copper plating solution are accurately measured, and the concentration of the copper ions is ensured to be in the optimal range, so that the quality of copper plating can be ensured. The traditional iodometry and coordination titration methods cannot meet the requirements of analysis work, for example, the terminal of the coordination titration method is difficult to observe, so that the sensitivity is not high, and the accuracy of the iodometry is not high. However, the spectrophotometry is considered as an ideal analytical detection method, and the method has high requirements for the precision of the instrument, and requires a microcomputer to process data, so that the wide application of the method is limited.
Disclosure of Invention
The invention aims to provide a method for detecting the concentration of copper ions in an acidic copper plating solution. The invention adopts an electrochemical method, and the adopted embedded microelectrode can avoid the defects of the traditional microdisk electrode, the traditional microelectrode repeatedly deposits in copper plating solution to cause copper on the surface of the microelectrode to overflow and can not be completely dissolved out, and the embedded electrode can avoid the problem.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a method for detecting the concentration of copper ions in an acidic copper plating solution. An electrochemical three-electrode testing system (an embedded microelectrode is used as a working electrode) is adopted, and the measurement is carried out by combining cyclic voltammetry.
And measuring the content of copper ions by taking the embedded micro-electrode as a working electrode and recording a cyclic voltammetry curve of a three-electrode system according to the oxidation peak and reduction peak currents of the cyclic voltammetry curve. Wherein, the working electrode used in the three-electrode system is an embedded microelectrode, and the diameter range of the electrode wire of the microelectrode is 1-500 μm. The electrode wire of the micro-electrode includes, but is not limited to, gold, silver, platinum, iridium, palladium, etc. The invention can be applied to the detection of other metals such as zinc, tin, chromium, nickel, etc. When the acid copper plating solution contains the accelerating agent, the inhibiting agent and the leveling agent, the detection of copper ions is not influenced.
The main innovative technology of the invention is as follows: the embedded microelectrode prepared by the invention avoids the defects of the traditional microelectrode, the traditional microdisk electrode can cause the growth of copper on the surface of the microdisk electrode due to repeated deposition or dissolution in copper plating solution, and the embedded microelectrode can avoid the problem. Under the existence of copper ions with different concentrations, the current values of the oxidation peak and the reduction peak of the cyclic voltammogram of the plating solution are different, so that the linear relation between the peak current and the copper ion concentration can be obtained.
Preparing an embedded microelectrode: the preparation method of the microelectrode adopts a king water soaking method. Soaking a capillary glass microelectrode by using aqua regia, and simultaneously soaking glass at the top end of the microelectrode and an electrode wire in the aqua regia for etching to obtain the embedded microelectrode.
The action principle of the embedded microelectrode is as follows: FIG. 1 is a cross-sectional view of a conventional micro-electrode and an embedded micro-electrode. The recent popularity of microelectrodes stems from its three advantageous properties. First, due to their small size, they can be introduced into systems where large size electrodes cannot enter. Second, microelectrodes maintain a constant potential, reaching or approaching a diffusion steady state for an experimentally accessible time, whereas for macroscopic electrodes, steady state currents can usually only be achieved by convective diffusion transport. Third, the ohmic polarization effect of the micro-electrode may be significantly reduced, and thus the experiment may be performed with a greatly reduced supporting electrolyte concentration. However, the conventional micro-electrode has some defects in copper plating solution analysis, such as the overflow of copper particles on the surface of the electrode due to repeated deposition when copper ions are analyzed by voltammetry, and cannot be completely dissolved, because the overflowing copper particles cannot contact with the micro-disk electrode and thus cannot be dissolved. While embedded microelectrodes can avoid this problem: the copper deposited in the embedded grooves is capable of directly contacting the microdisk, so that the copper is very rapidly deposited and dissolved out of the grooves, and the copper particles are prevented from overflowing.
The detection method of copper ions in the plating solution comprises the following steps: in the acidic copper plating solution, an embedded microelectrode is used as a working electrode to carry out cyclic voltammetry scanning, and the copper ion concentration is calculated according to the oxidation peak, reduction peak current or peak area of the cyclic voltammetry.
The invention has the advantages that:
the traditional copper ion detection method has the limitations that the operation is complex and the accuracy is low, and the method is simple and convenient to operate and has good accuracy. The main innovative technology of the invention is as follows: the embedded microelectrode prepared by the invention avoids the defects of the traditional microdisk electrode, and the traditional microdisk electrode is repeatedly deposited in copper plating solution, so that copper on the surface of the microelectrode overflows and cannot be completely dissolved out, and the detection precision is influenced; and the embedded microdisk electrode can avoid this problem. And (3) rapidly and accurately detecting copper ions in the acidic copper plating solution by using a deposition peak and a dissolution peak of a cyclic voltammetry method.
Another advantage of the present invention is: the method can be directly used for detecting the copper ions in the acidic copper plating solution without sample pretreatment. Other complex components in the bath such as various additives: the inhibitor, the accelerant, the brightener, the leveling agent and the like have no influence on the detection of the copper ions, and the concentration range of the copper ions detected by the method basically comprises the concentration of the copper ions used in the traditional copper plating process.
Drawings
FIG. 1 shows (a) a schematic diagram of a conventional microelectrode, (b) a schematic diagram of an embedded microelectrode, and (c) a physical diagram of an embedded structure on top of the embedded microelectrode.
FIG. 2 is a sectional view of a conventional micro-electrode (b) and an embedded micro-electrode (c), a represents an electrode radius,Lindicating the embedding depth.
FIG. 3 shows (a) the embedded gold microelectrode in an acidic copper plating bath (containing different concentrations of Cu)2+5-70 g/L), the composition of the acid copper plating solution: cu2+Concentration: 5,10,20,30,40,50,60,70 g/L. 0.5M H2SO4, 20 ppm Cl-300 ppm PEG, 8 ppm MPS, 10 ppm JGB. (b) And (3) linearly fitting the peak current of a reduction peak (A peak) and an oxidation peak (B peak) of a CV diagram of the embedded gold microelectrode with the concentration of copper ions in the acid copper plating solution.
FIG. 4 shows (a) conventional gold microelectrodes (25 μ M in diameter) in acidic copper plating baths (containing varying concentrations of Cu)2+CV diagram in 5-70 g/L), acid copper plating solution composition: cu (copper)2+Concentration: 5,10,20,30,40,50,60,70 g/L. 0.5M H2SO4, 20 ppm Cl-300 ppm PEG, 8 ppm MPS, 10 ppm JGB. (b) Linear fitting of the peak current of the reduction peak (A peak) and the oxidation peak (B peak) of the CV diagram of a conventional gold microelectrode (diameter 25 μ M) in an acidic copper plating solution to the concentration of copper ions.
Detailed Description
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanying figures are described in detail below. The method of the present invention is a method which is conventional in the art unless otherwise specified.
According to the method for detecting the concentration of copper ions in the acid plating solution, firstly, the capillary glass microelectrode is soaked in aqua regia, and the glass at the top end of the microelectrode and an electrode wire need to be simultaneously immersed in the aqua regia for etching to obtain the embedded microelectrode. A three-electrode electrochemical testing system (an embedded microelectrode is used as a working electrode) is adopted, and the measurement is carried out by combining cyclic voltammetry. The embedded microelectrode comprises a glass capillary tube and an electrode wire, the diameter range of the electrode wire of the microelectrode is 1-500 mu m, and the electrode wire comprises but is not limited to gold, silver, platinum, iridium, palladium and the like.
1. Preparing acid copper plating solution containing different copper ion concentrations: contains copper sulfate, sulfuric acid, inhibitor, promoter and leveling agent. The concentration of copper ions in the acid copper plating solution is 5 g/L-70 g/L.
2. Cyclic voltammetry test conditions: the potential range is-0.7V-1.5V (vs. SHE), the sweep rate range is: 0.01 to 5.0V/s.
3. Drawing a fitting curve: and respectively taking the current of the oxidation peak and the reduction peak of the cyclic voltammogram to be linearly fitted with the concentration of the copper ions to obtain a standard curve for detecting the copper ions.
4. And (3) analyzing the concentration of the plating solution: preparing acidic copper plating solutions with different concentrations of copper ions, performing cyclic voltammetry scanning by using an embedded microelectrode to obtain oxidation peak and reduction peak currents, and substituting the oxidation peak and reduction peak currents into a standard curve to calculate the copper ion concentration.
Example 1
Preparing an embedded microelectrode: soaking a capillary glass microelectrode by using aqua regia, and simultaneously soaking glass and an electrode wire at the top end of the microelectrode in the aqua regia for etching to obtain the embedded microelectrode. The embedded microelectrode comprises a glass capillary tube and a wire electrode, wherein the wire electrode of the microelectrode is gold, the diameter of the wire electrode is 25 mu m, and the embedding depth of the wire electrode is 60 mu m. The depth of insertion refers to the distance from the top of the wire to the top of the glass.
The provided method for detecting the concentration of copper ions in the acidic plating solution comprises the following steps: the measurement is carried out by adopting a three-electrode electrochemical test system (an embedded gold microelectrode is used as a working electrode in the three-electrode system, copper/copper sulfate (saturated copper sulfate solution is used as internal filling liquid) is used as a reference electrode, and a platinum wire is used as a counter electrode) in combination with a cyclic voltammetry. The specific test method comprises the following steps:
1. preparing acid copper plating solution containing different copper ion concentrations: respectively contains 5,10,20,30,40,50,60,70 g/L copper ions and 0.5M H2SO4，20 ppm Cl-，300 ppm PEG，8 ppm MPS，10 ppm JGB。
2. Cyclic voltammetry test conditions: the potential range is-0.7V-1.5V (vs. Cu/CuSO)4) The sweeping speed is 0.4V/s. The measured CV is shown in FIG. 3 (a).
3. Drawing a fitting curve: and respectively taking the current values of the reduction peak (A peak) and the oxidation peak (B peak) of the cyclic voltammogram to be linearly fitted with the concentration of the copper ions to obtain a standard curve for detecting the copper ions. The peak currents of the reduction peak and the oxidation peak of CV in (a) of fig. 3, i.e., the a peak and the B peak, can both have a linear relationship with the copper ion concentration, the linear correlation coefficients are 0.992 and 0.979 (B in fig. 3), and the two standard curves are y = -0.038 x +0.0172 and y =0.041x +0.787, respectively.
TABLE 1 values of oxidation peak and reduction peak current corresponding to different concentrations of copper ion in embedded microelectrode
4. And (3) analyzing the concentration of the plating solution: preparing acidic copper plating solutions with different concentrations of copper ions, wherein the plating solutions respectively contain 8, 24 and 36 g/L of copper ions and 0.5M H2SO4，20 ppm Cl-，300 ppm PEG，8 ppm MPS, 10 ppm JGB. And (3) carrying out cyclic voltammetry scanning by using an embedded microelectrode to obtain current values of a peak A and a peak B, substituting the current values into a standard curve to calculate the concentration of copper ions, wherein the embedded microelectrode is used for multiple times in advance. "Cu" in Table 22+The concentration calculation value is two Cu values calculated after the current values of the A peak and the B peak are respectively substituted into two standard curves2+Average value of concentration. In practical application, according to the same method, firstly, the embedded microelectrode is subjected to cyclic voltammetry scanning to obtain two peak current values, and then the two peak current values are substituted into two standard curves to obtain two Cu values through calculation2+The concentration is averaged to obtain the concentration of the copper ions.
TABLE 2 Embedded microelectrode for detection of copper ions of varying concentrations
Comparative example 1
The method for detecting the concentration of copper ions in the acid plating solution by using the traditional microelectrode comprises the following steps: the measurement was carried out using a three-electrode electrochemical test system (using a conventional gold microelectrode (diameter 25 μm) as the working electrode) in combination with cyclic voltammetry. The specific test method comprises the following steps:
1. preparing acid copper plating solution containing different copper ion concentrations: respectively contains 5,10,20,30,40,50,60,70 g/L copper ions and 0.5M H2SO4，20 ppm Cl-，300 ppm PEG，8 ppm MPS，10 ppm JGB。
2. Cyclic voltammetry test conditions: the potential range is-0.7V-1.5V (vs. Cu/CuSO)4) Sweeping speed: 2V/s, and the CV diagram measured is shown in FIG. 4 (a).
3. Drawing a fitting curve: and respectively taking the current values of the reduction peak (A peak) and the oxidation peak (B peak) of the cyclic voltammogram to be linearly fitted with the concentration of the copper ions to obtain a standard curve for detecting the copper ions. The peak currents of the reduction peak and the oxidation peak of CV in (a) of fig. 4, i.e., the a peak and the B peak, can have a linear relationship with the copper ion concentration, and the linear correlation coefficients are 0.9957 and 0.851 (B in fig. 4), respectively, and the two standard curves are y =0.1184-0.1573x, and y =10.411+0.3621x, respectively.
TABLE 3 corresponding values of oxidation peak and reduction peak current for conventional gold microelectrodes (25 μm) at different concentrations of copper ion
4. And (3) analyzing the concentration of the plating solution: preparing acidic copper plating solutions with different concentrations of copper ions, wherein the plating solutions respectively contain 8, 24 and 36 g/L of copper ions and 0.5M H2SO4，20 ppm Cl-300 ppm PEG, 8 ppm MPS, 10 ppm JGB. And (3) carrying out cyclic voltammetry scanning by using a traditional microelectrode to obtain current values of a peak A and a peak B, substituting the current values into a standard curve to calculate the concentration of copper ions, wherein the traditional microelectrode is used for multiple times in advance. "Cu" in Table 42+The calculated concentration value is two Cu values calculated after the current values of the peak A and the peak B are respectively substituted into the two standard curves2+Average value of concentration. In practical application, according to the same method, the traditional microelectrode is subjected to cyclic voltammetry scanning to obtain two peak current values, and then the two peak current values are substituted into two standard curves to obtain two Cu values2+The concentration is averaged to obtain the concentration of the copper ions.
TABLE 4 conventional microelectrodes for detecting copper ions of different concentrations
The above description is only a preferred embodiment of the present invention, and all the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (5)
1. A method for detecting the concentration of copper ions in an acidic copper plating solution is characterized in that an electrochemical three-electrode testing system is adopted, the copper ions in the acidic copper plating solution are measured by combining cyclic voltammetry, and a working electrode in the three-electrode testing system is an embedded microelectrode.
2. The method of claim 1, wherein the copper metal ion concentration is detected by recording a cyclic voltammogram of the three-electrode test system from a plot of the oxidation peak, reduction peak current, or peak area of the cyclic voltammogram versus copper ion concentration.
3. The method of claim 1, wherein the embedded microelectrode is prepared by a method comprising: soaking a capillary glass microelectrode by using aqua regia, and simultaneously soaking glass at the top end of the microelectrode and an electrode wire in the aqua regia for etching to obtain an embedded microelectrode; the embedded microelectrode comprises a glass capillary tube and a wire electrode, the diameter range of the wire electrode of the microelectrode is 1-500 mu m, the wire electrode material comprises one of gold, silver, platinum, iridium and palladium, and the embedding depth is 1-10 times of the diameter of the wire electrode.
4. The method of claim 1, wherein the cyclic voltammetry test conditions are: the potential range is-0.7V-1.5V (vs. SHE), and the sweep rate range is as follows: 0.01 to 5.0V/s.
5. The method of claim 1, wherein the detection method is applied to detection of concentrations of a plurality of metal ions, including but not limited to copper ions, zinc ions, tin ions, silver ions.
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