CN117825322A - Method for measuring copper sulfate pentahydrate in electroplating bath working solution - Google Patents
Method for measuring copper sulfate pentahydrate in electroplating bath working solution Download PDFInfo
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- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000009713 electroplating Methods 0.000 title claims description 71
- 239000012224 working solution Substances 0.000 title description 10
- 238000007747 plating Methods 0.000 claims abstract description 59
- 238000005259 measurement Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000002835 absorbance Methods 0.000 claims description 80
- 230000003287 optical effect Effects 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005282 brightening Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 238000012360 testing method Methods 0.000 abstract description 29
- 238000004448 titration Methods 0.000 abstract description 26
- 239000000243 solution Substances 0.000 description 57
- 239000000523 sample Substances 0.000 description 56
- 239000010949 copper Substances 0.000 description 48
- 238000004458 analytical method Methods 0.000 description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 229910052802 copper Inorganic materials 0.000 description 27
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 22
- 238000002798 spectrophotometry method Methods 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 15
- 230000002378 acidificating effect Effects 0.000 description 13
- 229910000365 copper sulfate Inorganic materials 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 239000007853 buffer solution Substances 0.000 description 10
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000691 measurement method Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
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- 239000002253 acid Substances 0.000 description 6
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- 239000012086 standard solution Substances 0.000 description 5
- 238000003556 assay Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000000540 analysis of variance Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention provides a method for measuring pentahydrate copper sulfate in plating bath working tank liquor, which adopts a spectrophotometer to measure the content of pentahydrate copper sulfate in the plating bath working tank liquor to be measured, wherein the content range of pentahydrate copper sulfate in the plating bath working tank liquor to be measured is 150-250g/L, and the characteristic wavelength adopted in the measurement of the pentahydrate copper sulfate by the spectrophotometer is 800-900nm. The determination method provided by the invention solves the problems of inaccurate test result, high cost and unfriendly environment in the prior art for determining the content of the copper sulfate pentahydrate in the working tank liquid by adopting a titration method.
Description
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to a method for measuring pentahydrate copper sulfate in a working bath solution of an electroplating bath.
Background
Electroplating is to plate a thin layer of other metal or alloy on the surface of some metal by electrolysis, and to adhere a metal film on the surface of metal or other material by electrolysis, so as to prevent oxidation and corrosion of metal, improve wear resistance, conductivity, reflectivity, corrosion resistance and beautiful appearance.
The electrolytic copper plating is the most main method for realizing electrical interconnection in electronic products, the acid copper plating is also called anode-process copper plating, and is a common electrolytic copper plating process, and during electroplating, the plating metal Cu is taken as an anode, and the anodeThe Cu is oxidized into cations by two electrons and enters the electroplating solution; an electronic part such as a PCB is a metal product to be plated as a cathode, cu in an electroplating solution 2+ The cations lose two electrons on the surface of the PCB and are reduced to form Cu, so that a copper plating film is formed.
The working tank liquid of the electroplating tank adopted in the electroplating acidic copper plating process is generally liquid containing pentahydrate copper sulfate, and Cu of the pentahydrate copper sulfate 2+ Under the action of direct-current voltage, the electrons are continuously transferred to the cathode (the plated piece), and finally the electrons are reduced to metallic copper on the cathode (the plated piece), so that a metallic copper plating layer or a circuit is gradually formed. In order to control the thickness of the plating layer formed on the final product, the plating speed is controlled, so that the Cu in the working bath of the plating bath is generally required 2+ Concentration control, cu is provided in most of the current electroplating acid copper plating processes 2+ The main salt of (C) is generally copper sulfate pentahydrate, and CuSO in the working tank solution of the electroplating tank is treated 4 ·5H 2 The concentration of O can be controlled to realize Cu 2+ And (3) controlling the concentration.
In the electroplating acid copper plating process of the circuit board, the content of the pentahydrate copper sulfate in the working tank liquid of the electroplating tank is up to 200+/-10 g/L, and the concentration is generally measured by adopting an EDTA titration method when the concentration is analyzed and measured in the prior art because of higher concentration. The method comprises the following specific steps: firstly, 1ml of electroplating bath working solution is taken into a 250ml glass conical flask, and 50ml of deionized water is added; then 5ml of buffer solution at ph=10 and 3 drops of PAN indicator are added in sequence; then, titration is carried out by using 0.05mol/L EDTA standard solution, the titration end point is the titration end point when the color is changed from purple to green, and the titration volume A is recorded; finally, the concentration of the copper sulfate pentahydrate is calculated, and the calculation formula of the concentration is C=A 0.05×249.685.
When the EDTA titration method is adopted to measure the content of the pentahydrate copper sulfate in the working bath solution of the electroplating bath, the method has the following defects:
firstly, a titration end point is judged by observing color change by naked eyes, the end point color is not easy to observe and judge, the difference of the titration volume of standard solution EDTA in different time periods of the same or different personnel is easy to cause, the titration volume A is inaccurate, the concentration calculation formula of the copper sulfate pentahydrate is C=A.12.48, the error of the titration volume A can cause further increase of the concentration deviation of the copper sulfate pentahydrate under the amplification of a coefficient of 12.48, and the titration method cannot accurately reflect the accurate content of the copper sulfate pentahydrate in the working tank liquid of the electroplating bath.
Secondly, besides the copper sulfate pentahydrate, impurity ions such as zinc, calcium, iron and the like exist in the working tank liquor of the electroplating tank, and an EDTA titration method in the prior art does not exist as a masking agent, so that the impurity ions interfere with a titration end point, the titration volume is enlarged, and the problem of higher measurement results occurs.
These drawbacks all affect the stability, reproducibility and reproducibility (GR & R) of the analysis results of the determination of the content of copper sulphate pentahydrate in the working bath of the plating bath.
In addition, the EDTA titration method has other defects, such as high consumption of EDTA-2Na standard solution and high use cost; the analysis process uses a buffer solution with pH=10, and the main component of the buffer solution is NH of 54g/L 4 Cl, NH at 35ml/L 3 ·H 2 O, which results in laboratory waste liquid discharge with higher ammonia nitrogen content.
The substance acts with light and has the characteristic of selective absorption. The color of the colored substance is a result of the substance reacting with light. I.e. the color exhibited by the colored solution is due to the selective absorption of light by the substances in the solution. Because different substances have different molecular structures and different absorption capacities for light with different wavelengths, a structural group with a characteristic structure exists, and the maximum actual receiving wavelength with the absorption characteristic is selected to form a maximum absorption peak, so that a specific absorption spectrum, namely a characteristic spectrum, is generated, and is an analysis principle of a spectrophotometry. Spectrophotometry is a method of qualitatively and quantitatively analyzing a substance to be measured by measuring the absorbance (Abs) of light at a specific wavelength or within a range of wavelengths. The method has the advantages of high sensitivity, simple and convenient operation, rapidness and the like, and is the most commonly used experimental method in biochemical experiments. The prior art also discloses another method for measuring the content of copper sulfate in the acidic copper plating solution by adopting a spectrophotometry, and the method aims at the copper sulfate content in the range of 0-4g/LMeasurement of copper sulfate content in the acidic copper plating solution. In the determination method, the acid copper plating solution is added with the color developing solution to ensure that Cu of a sample to be detected 2+ Complexing with EDTA in alkaline environment with pH 9-10 to obtain characteristic structural group Cu 2+ A solution of EDTA, in which the concentration of copper sulphate and the absorbance follow the lambert-beer law, and in which spectrophotometry can be used to analyze the copper sulphate content, characteristic structural groups Cu 2+ EDTA has a characteristic wavelength of 750nm. Wherein, the components of the color development liquid are as follows: EDTA (50 g/l), NH 4 Cl(70g/L)、NH 3 ·H 2 O (570 ml/L), deionized water, which acts as follows: adjusting the pH of the acidic copper-plated sample to an optimum pH of 9-10; cu of EDTA and copper sulfate pentahydrate 2+ And (5) complex color development.
The specific operation steps are as follows: firstly, drawing a copper sulfate standard curve, weighing 2.5g of superior pure copper sulfate (CuSO4.5H20), dissolving in a proper amount of water, transferring into a 250mL volumetric flask, adding water to a constant volume, and uniformly mixing. The standard solution contained 10mg/mL copper sulfate. Then, respectively taking 0.5, 1, 1.5, 2, 3 and 4mL of 10mg/mL copper sulfate standard solution to a 10mL colorimetric tube, adding 2mL of color development liquid, and fixing the volume to 10mL by deionized water to prepare standard samples with the concentration of 0.5, 1, 1.5, 2, 3 and 4mg/mL respectively; then, the absorbance of each standard sample is measured on a spectrophotometer with a characteristic wavelength of 750nm and a cuvette with an optical path of 1cm by taking water as a reference, and a standard curve is drawn according to the concentration-absorbance or a regression equation is given. And finally, taking a certain amount of sample to be measured into a 10ml colorimetric tube, adding 2ml of color reagent, measuring the absorbance of the sample to be measured, and finding out or calculating the content of copper sulfate in the sample to be measured according to a regression equation from a standard curve.
The spectrophotometry method for measuring the content of the copper sulfate has the following defects: the pH of the sample to be tested is adjusted to be within the optimal range of 9-10 by using a developing solution, and Cu is influenced by too large or too small pH adjustment 2+ Complexing EDTA to give Cu 2+ The stability of EDTA, leading to inaccurate analysis results; the usage amount of EDTA also determines whether Cu in the copper sulfate of the sample to be tested can be removed 2+ Complete complexation to Cu 2+ Incomplete complexation of EDTA leads to inaccurate analysis results and, likewise, excessive EDTAThe effect was not elucidated. In addition, this method also has the problem of excessive cost caused by the use of EDTA, and the buffer solution, the main component of which includes NH, is used in the analysis process 4 Cl and NH 3 ·H 2 O, which results in laboratory waste liquid discharge with higher ammonia nitrogen content.
Disclosure of Invention
The invention aims to provide a method for measuring copper sulfate pentahydrate in a working tank liquid of an electroplating tank, which aims to solve the problems of inaccurate measurement result, high cost and environmental friendliness of the titration method for measuring the content of the copper sulfate pentahydrate in the working tank liquid in the prior art.
In order to solve the technical problems, the invention provides a method for measuring the copper sulfate pentahydrate in the working bath solution of an electroplating bath, which adopts a spectrophotometer to measure the content of the copper sulfate pentahydrate in the working bath solution of the electroplating bath to be measured, wherein the content range of the copper sulfate pentahydrate in the working bath solution of the electroplating bath to be measured is 150-250g/L, and the characteristic wavelength adopted in the measurement of the copper sulfate pentahydrate by the spectrophotometer is 800-900nm.
Further, a cuvette used in the measurement by a spectrophotometer is a quartz cuvette, and the optical path is 1mm.
Further, the measurement method specifically includes:
s1: drawing a concentration-absorbance curve of a copper sulfate pentahydrate standard sample;
s2: taking working tank liquid of the plating tank to be measured into a cuvette of a spectrophotometer, and measuring absorbance of the working tank liquid of the plating tank to be measured by a machine;
s3: and obtaining the content of the copper sulfate pentahydrate in the working tank solution of the plating tank to be tested according to the concentration-absorbance curve and the absorbance of the working tank solution of the plating tank to be tested.
Further, the content range of the pentahydrate copper sulfate in the working tank liquid of the plating tank to be tested is 180-220g/L.
Further, the content range of the copper sulfate pentahydrate in the working bath solution of the plating bath to be tested is 190-210g/L.
Further, the characteristic wavelength used in the measurement is 800-850nm.
Further, the characteristic wavelength used in the measurement is 800-820nm.
Further, the S1 specifically includes: and (3) obtaining the absorbance of at least 3 copper sulfate pentahydrate standard samples with different concentrations, then fitting a straight line by taking the concentration of the copper sulfate pentahydrate standard samples as an abscissa and the absorbance of the copper sulfate pentahydrate standard samples as an ordinate, and obtaining the concentration-absorbance curve.
Further, the S1 specifically includes: and (3) obtaining the absorbance of at least 5 copper sulfate pentahydrate standard samples with different concentrations, then fitting a straight line by taking the concentration of the copper sulfate pentahydrate standard samples as an abscissa and the absorbance of the copper sulfate pentahydrate standard samples as an ordinate, and obtaining the concentration-absorbance curve.
Further, the standard sample of the copper sulfate pentahydrate comprises copper sulfate pentahydrate, sulfuric acid, chloride ions, a brightening agent, a carrier and a leveling agent.
In summary, the invention provides a method for measuring the pentahydrate copper sulfate in the working bath solution of the electroplating bath, which can overcome the defects of the conventional EDTA titration method measurement analysis system, does not need to use EDTA for titration, avoids errors caused by artificial judgment of a titration end point, can improve analysis precision and stability, does not need additional reagents and buffer solution, reduces analysis cost, and reduces the emission of ammonia nitrogen in wastewater. At the same time, compared with the spectrophotometry in the prior art, the method combines the color reagent with Cu 2+ Method for measuring concentration, which can avoid color former and Cu 2+ The reaction is incomplete or excessive, so that the measurement result is inaccurate, and the additional reagent and buffer solution are not needed, thereby reducing the analysis cost and reducing the emission of ammonia nitrogen in the wastewater.
In addition, the measuring method provided by the invention can directly analyze the content of the copper sulfate pentahydrate in the electroplating acidic copper plating solution by using the working solution under the condition of not changing the property of the working solution of the electroplating bath, is simple and quick, and the stability of the whole measuring and analyzing system meets the requirements of GR & R less than or equal to 10%, and the requirements of linearity less than 10%, offset less than 10% and P >0.05, so that the measuring method is a reliable analyzing method with practicability.
Drawings
FIG. 1 is a schematic flow chart of a method for measuring copper sulfate pentahydrate in a working bath solution of an electroplating bath according to an embodiment of the invention;
FIG. 2 is a graph showing absorption curves of copper sulfate pentahydrate samples at different wavelengths at different concentrations in an embodiment of the present invention;
FIG. 3 is a graph showing the concentration mean distribution of each test group in the measurement stability test according to the embodiment of the present invention;
FIG. 4 is a graph showing concentration range profiles of each test group in a stability test according to an embodiment of the present invention;
FIGS. 5 and 6 are graphs of measurements R & R (analysis of variance) reports for each test group measurement in a reproducibility test in accordance with embodiments of the present invention;
FIG. 7 is a graph of a linear and offset analysis report of the results of each test group in the linear and offset test according to the embodiment of the present invention.
Detailed Description
The method for measuring the copper sulfate pentahydrate in the working bath solution of the electroplating bath provided by the invention is further described in detail below with reference to the accompanying drawings and the specific embodiments. The advantages and features of the present invention will become more apparent from the following description.
It should be noted that the drawings are in a very simplified form and are all to a non-precise scale, merely for the purpose of facilitating and clearly aiding in the description of embodiments of the invention. For a better understanding of the invention with objects, features and advantages, refer to the drawings.
In this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The spectrophotometry in the prior art can measure the copper sulfate content in the acidic copper plating solution by aiming at the copper sulfate content within the range of 0-4g/L, and the spectrophotometry adopts the chromogenic solution and Cu 2+ Bonding to obtain Cu 2+ EDTA-characteristic groups, having an absorption peak at 750nm. However, this solution has the disadvantages of inaccurate measurement, high reagent cost and environmental unfriendly. In addition, according to the scheme, aiming at the plating bath solution with higher copper sulfate content, the plating bath solution needs to be diluted and then is measured on the machine, so that the measurement error is larger.
In the electroplating acidic copper plating process in the circuit board industry, a working solution containing pentahydrate copper sulfate is mostly adopted as an electroplating bath working solution, and the plating solution is blue due to the characteristic structural group of the pentahydrate copper sulfate. Based on the above, the inventor provides a scheme for directly measuring the working bath solution of the electroplating bath by using a spectrophotometry without dilution and other treatments through a large number of experiments, and the scheme can solve the problem of measurement errors caused by the need of pretreatment of the working bath solution of the electroplating bath in the prior art, and can also solve the problems of high cost and unfriendly environment of the existing measurement method.
Specifically, the invention provides a method for measuring copper sulfate pentahydrate in a plating bath working tank solution, which adopts a spectrophotometer to measure the content of the copper sulfate pentahydrate in the plating bath working tank solution to be measured, wherein the content range of the copper sulfate pentahydrate in the plating bath working tank solution to be measured is 150-250g/L, and the characteristic wavelength adopted in the measurement by the spectrophotometer is 800-900nm.
In the technical scheme provided by the invention, based on the principle of spectrophotometry, cuSO which presents blue color per se in the working tank liquid of the electroplating tank is analyzed 4 ·5H 2 Whether the O group can be used as a characteristic group for spectrophotometrically measuring absorbance, namely analyzing CuSO without adding additional auxiliary reagents into the working bath solution of the electroplating bath and changing the structure of each component in the bath solution 4 ·5H 2 Whether the blue color represented by the O group has characteristic wavelength or wave band, and whether the absorbance of the blue color is in line with that of the blue colorAnd follows lambert-beer's law.
The inventors have conducted a number of experiments to find that when the plating tank is operated with CuSO in the bath solution 4 ·5H 2 At low O levels, the absorption peak is not pronounced, i.e., when CuSO is in solution 4 ·5H 2 When the O content is low, the method is not suitable for directly carrying out on-machine measurement on absorbance of the solution on a spectrophotometer. And only when CuSO 4 ·5H 2 When the content of O reaches a certain concentration, a more obvious absorption peak appears, and the corresponding characteristic wavelength range in the absorption curve is narrower. In the current electroplating acid copper plating process in the circuit board industry, the concentration range of the pentahydrate copper sulfate in the electroplating bath working tank solution is about 150-250g/L, and aiming at the concentration range, the inventor finds that the characteristic wavelength range of the absorbance measured directly by the electroplating bath working tank solution on a spectrophotometer is 800-900nm, and the CuSO in the electroplating bath working tank solution is within the range 4 ·5H 2 The absorption peak of the O group is obvious, and the O group can be directly used for spectrophotometry on-machine measurement of absorbance, thereby measuring CuSO in the working tank liquid 4 ·5H 2 O content.
The measuring method provided by the invention can be used for overcoming the defects of the conventional EDTA titration measuring and analyzing system, does not need to adopt EDTA for titration, avoids errors caused by artificial judgment of a titration end point, can improve the analysis precision and stability, does not need additional reagents and buffer solution, reduces the analysis cost and reduces the emission of ammonia nitrogen in wastewater. At the same time, compared with the spectrophotometry in the prior art, the method combines the color reagent with Cu 2+ Method for measuring concentration, which can avoid color former and Cu 2+ The reaction is incomplete or excessive, so that the measurement result is inaccurate, and the additional reagent and buffer solution are not needed, thereby reducing the analysis cost and reducing the emission of ammonia nitrogen in the wastewater.
Further, when the absorbance of the liquid to be measured is too small, the photometric noise is increased, and further the analysis error is increased; if the absorbance of the liquid to be measured is too large, the analysis error is increased due to stray light. In order to avoid that the absorbance value of the solution to be measured is not in the optimal range (generally 0.3-0.7 Abs), the selection of the cuvette is optimized, the quartz cuvette with the optical path of 1mm is preferably adopted, the middle cuvette is used, so that the working bath solution of the electroplating bath with the copper sulfate pentahydrate content range of 150-250g/L can be directly subjected to on-machine measurement, the absorbance value can be in the optimal range, and the measurement error is reduced.
Specifically, as shown in fig. 1, the specific steps of the measurement method provided by the present invention may include:
s1: drawing a concentration-absorbance curve of a copper sulfate pentahydrate standard sample; firstly preparing a plurality of copper sulfate pentahydrate standard sample solutions with different concentrations, wherein the components of the copper sulfate pentahydrate standard sample solutions are the same as the components in the working tank liquid of the electroplating tank to be tested, and the copper sulfate pentahydrate standard sample solutions can comprise copper sulfate pentahydrate, sulfuric acid, chloride ions, brightening agent, carrier, leveling agent and the like. In the configuration, 3 or 5 standard samples with different concentrations, preferably more than 5 standard samples, can be configured, so that concentration-absorbance data of more standard samples can be acquired as much as possible, a fitted curve is more accurate, and the measurement accuracy is improved. The content of other components except the content of the copper sulfate pentahydrate in the standard samples with different concentrations is the same. After preparing standard samples with different concentrations, taking the standard samples, placing the standard samples into a cuvette, taking deionized water as a reference, obtaining absorbance data of a plurality of standard samples, then taking the concentration of the copper sulfate pentahydrate standard sample as an abscissa, taking the absorbance of the copper sulfate pentahydrate standard sample as an ordinate, and fitting a straight line to obtain a concentration-absorbance curve or a linear regression equation.
S2: taking working tank liquid of the plating tank to be measured into a cuvette of a spectrophotometer, and measuring absorbance of the working tank liquid of the plating tank to be measured by a machine;
s3: and obtaining the content of the copper sulfate pentahydrate in the working tank solution of the plating tank to be tested according to the concentration-absorbance curve and the absorbance of the working tank solution of the plating tank to be tested.
When the method is adopted to accurately measure the content of the copper sulfate pentahydrate in the working tank liquid of the electroplating tank to be measured, the content range of the copper sulfate pentahydrate in the working tank liquid can be 150-250g/L, preferably 180-220g/L, more preferably 190-210g/L, and the method is more close to the content range of the copper sulfate pentahydrate in the working tank liquid of the actual electroplating tank. The sample is selected to have a characteristic wavelength of 800-900nm, preferably 800-850nm, more preferably 800-820nm, when measured on a spectrophotometer.
In order to further understand the present invention, the measurement method according to the present invention will be evaluated in conjunction with more detailed embodiments, so as to highlight the features and characteristics of a measurement method for copper sulfate pentahydrate in a working bath solution of an electroplating bath according to the present invention. The description is only intended to illustrate the features and advantages of the assay method of the invention and is not intended to limit the scope of the invention.
Example 1 characteristic wavelength assessment
In the measuring method, spectrophotometry is used for measuring the absorbance of the pentahydrate copper sulfate in the working bath liquid of the electroplating bath, and the content of the pentahydrate copper sulfate is obtained by combining the concentration-absorbance curve of the standard sample. Spectrophotometry is used to verify whether the copper sulfate pentahydrate groups in the solution follow lambert-beer law and determine the absorption spectrum.
Based on this, this example 1 was configured with copper sulfate pentahydrate samples of different concentrations, and then absorbance data of the copper sulfate pentahydrate samples of different concentrations at different wavelengths was verified.
The configuration of the copper sulfate pentahydrate sample is shown in the following table 1, and in the copper sulfate pentahydrate sample, other components and contents are close to the component contents of the working bath solution of the electroplating bath in the actual electroplating acidic copper plating process except for the content of the copper sulfate pentahydrate.
TABLE 1 component content Table of copper sulfate pentahydrate samples
Among them, brightening agents, carriers and leveling agents are all commonly used in practical acid copper plating processes for electroplating, for example, brightening agents generally comprise sulfur-containing organic matters, and the main function in electroplating is to help copper ions accelerate reduction at a cathode, and simultaneously form new copper plating crystal nuclei (reduce surface diffusion deposition energy) so that a copper layer structure becomes finer. The carrier, also called carrier, is usually a high molecular weight polyol compound, and is adsorbed by the cathode surface and acts together with chloride ions to inhibit the plating rate, so that the difference between the high and low current areas is reduced (i.e., the polarization resistance is increased), and the electroplated copper can be uniformly and continuously deposited. Leveling agents are typically nitrogen-containing organic substances that have the primary function of adsorbing at the high current density areas (raised areas or corners) and slowing the plating rate at that point without affecting the plating at the low current density areas (recessed areas), thereby leveling the surface, which is an essential additive in plating.
Absorbance data for different concentrations of copper sulfate pentahydrate samples at different wavelengths are shown in table 2 below, wherein the cuvettes used are conventional 1cm path quartz cuvettes.
TABLE 2 absorbance data for copper sulfate pentahydrate samples of different concentrations at different wavelengths
From the data of table 2, fitting the concentration and absorbance data of samples of different concentrations at each wavelength, it was found that when monochromatic light radiation passes through the copper sulfate pentahydrate solution of the sample under test, the absorption of copper sulfate pentahydrate to light over a range of concentrations is proportional to the concentration, the relationship of which can be expressed by lambert-beer law: t=a×b×c, wherein each parameter means: t: absorbance, B: solution layer thickness (cm), cuvette optical path, C: concentration of the solution (g/dm) 3 ) And (A) the following steps: the absorbance, which is related to the nature of the solution, temperature, and wavelength.
The data of table 2 were used to fit the absorption curves of copper sulfate pentahydrate samples of different concentrations at different wavelengths to obtain the absorption curve diagram shown in fig. 2.
As can be seen from the results of FIG. 2, different contentsCuSO 4 ·5H 2 The absorption curve of the O sample is different, and the low-concentration CuSO is adopted 4 ·5H 2 The absorption peak of the O sample is not obvious, when CuSO 4 ·5H 2 When the content of O reaches a certain concentration (more than 50 g/L), a more obvious absorption peak appears, and the highest peak section appears between 800 and 900nm, namely the characteristic wavelength section is 800 to 900nm, and particularly, the absorption peak is more obvious when the content of O is 800 to 850nm.
In addition, according to lambert-beer law, factors influencing the absorbance of a sample are the concentration of the sample and the optical path length of a cuvette, and the absorption amount of the copper sulfate pentahydrate to the light is proportional to the concentration within a certain concentration range, so that the absorbance is an intuitive factor for reacting the concentration of the sample. The absorbance is an optimal choice in spectrophotometry for determining the concentration of a sample.
Since photometric noise is one of the main sources of analytical error, it limits the lower limit of absorbance of the sample being analyzed. If the absorbance value of the sample is too small (signal is small), the signal-to-noise ratio of the instrument may be lowered due to photometric noise, and an analysis error may be increased. When the photometric noise is large to a certain extent and the absorbance is small to a certain extent, the absorbance is not directly proportional to the concentration of the sample at all. Even when the sample concentration becomes thin, the absorbance value increases (due to noise) so that stable measurement data cannot be obtained. Therefore, the absorbance selection data cannot be too small.
Because stray light is one of the major sources of analytical error, it limits the upper limit of absorbance values of the sample being analyzed. If the absorbance of the sample is too large, an analysis error may be increased due to stray light. Because stray light can cause the analysis test result to deviate from beer's law seriously, the data of the analysis test result may be smaller or larger; if the stray light is absorbed by the sample, the measurement data is small, and if the stray light is not absorbed by the sample, the measurement data is large. If the stray light of the instrument is large, the absorbance is not directly proportional to the concentration of the sample at all, and even when the concentration of the sample is increased, the absorbance value is reduced instead, and other abnormal phenomena are generated. Therefore, the absorbance selection data cannot be too large.
In the industry, when spectrophotometry is used to measure absorbance of a sample, typically 0.3-0.7Abs is selected as the optimal selection range for absorbance. In general, in order to make the absorbance of a sample within the optimal range, when the concentration of the sample is too high, the sample is diluted, and when the concentration of the sample is too low, a cuvette with a larger optical path is selected to increase the absorbance value.
With reference to the data in table 1, we can see that, because the content of the pentahydrate copper sulfate in the working solution of the electroplating bath used in the actual electroplating acidic copper plating process is within the range of 200±10g/L, when the conventional cuvette with an optical path of 1cm is used, the absorbance value becomes very large, and due to the influence of stray light, the high-concentration sample cannot find specific stable absorbance within the range of characteristic wavelength 800-900nm, and the factors that the analysis error is increased by diluting the sample are considered.
For selection of cuvettes, a comparison test was also performed in this example 1, samples with proportions and contents close to those of the working tank solution of the electroplating tank were selected, and absorbance comparison tests were performed by using cuvettes with different optical paths.
The sample preparation is carried out according to the proportion shown in the following table 3, after the sample preparation, the absorbance data verification is carried out by using cuvettes with various optical paths on an upper machine, the characteristic spectrum is selected to be 800-900nm, and the obtained absorbance data are shown in the following table 4 by taking water as a reference.
TABLE 3 composition of samples
Table 4 comparison of absorbance data from different path cuvettes
According to the results of table 4, it can be seen that, according to the invention, aiming at the situation that the content of the pentahydrate copper sulfate in the working bath liquid of the electroplating bath used in the actual electroplating acidic copper plating process is higher, the optical path of the cuvette is optimized, and the quartz cuvette with the optical path of 1mm is selected, so that the absorbance test of an actual sample can be ensured to be carried out without dilution directly on the machine, the absorbance value is within the optimal value range, and the error influence caused by sample dilution is avoided.
The inventors have further carried out a supplemental test by using a quartz cuvette with an optical path of 1mm, and set samples with different concentrations in combination with the content of copper sulfate pentahydrate in the working bath solution of the electroplating bath used in the actual electroplating acidic copper plating process, and selected characteristic wavelengths of 800-900nm for absorbance test, and the configuration table of the samples is shown in the following table 5.
Table 5 Table of the composition ratios of the samples
Absorbance data for the 5 groups of samples are shown in table 6 below.
TABLE 6 absorbance data
As can be seen from the results of Table 6, when a quartz cuvette with an optical path of 1mm is used, the absorbance values of the sample solutions with concentrations ranging from 160g/L to 240g/L are substantially uniformly distributed within the optimum range of 0.3 to 0.7 Abs.
Example 2 reliability assessment of assay
According to the invention, the spectrophotometry is adopted to measure the content of the pentahydrate copper sulfate in the working bath liquid of the electroplating bath, and the reliability of the measuring method is required to be evaluated, so that the whole measuring and analyzing system meets the requirements of stability, reproducibility (GR & R) less than or equal to 10%, linearity <10%, offset <10% and P > 0.05.
When the measurement stability test is carried out, a standard sample solution is prepared, the concentration of the sample is measured according to the measuring method provided by the invention, 3 data are continuously measured every day to form 1 group, 25 groups of data are continuously measured in total, and the stability of the measurement result is observed. Wherein the standard sample solutions were prepared according to the configuration table of table 3, and the measured results are shown in table 7 below.
TABLE 7 stability test results of standard sample solutions
From the data of table 7, a mean result profile and a range profile of each of the 25 test groups can be obtained as shown in fig. 3 and 4, respectively.
As can be seen, the concentration mean deviation of each test group was maintained within.+ -. 1g/L, and the range of the range was not more than 2g/L. The measurement method provided by the invention is proved to meet the measurement requirement in measurement stability.
In the reproducibility (GR & R) test, this example 2 was performed by configuring 3 groups of test samples of different concentrations and then testing the copper sulfate pentahydrate content of the samples by three different analytical testers using the assay protocol provided by the present invention. The configuration table of 3 groups of test samples of different concentrations is shown in table 8 below.
TABLE 8GR & R test sample configuration Table
The concentration data of the samples measured by the three different analytical testers are shown in Table 9 below.
TABLE 9GR & R test sample test results
From the data of table 9, the measured value gauge R & R (analysis of variance) reports are shown in fig. 5 and 6.
As can be seen from a combination of the results of fig. 5 and 6, fig. 5 reflects the analysis of measurement errors of different testers/operators and the analysis of errors of the tools used by the different testers/operators when testing the sample, and it can be seen from the results that the analysis of errors of the sample, the average value and the different testers and the different components are all within the required range. Figure 6 shows the measurement error report of the measured value, and from the results given, the GR & r=4.41% of the measurement scheme provided by the invention meets the GR & R < 10%.
In the linear and offset test of this example 2, 5 test samples of different concentrations were prepared, and then 10 concentration determinations were performed for each test sample according to the determination method provided by the present invention. The configuration table of 5 test samples of different concentrations is shown in table 10 below.
Table 10 sample configuration table
The measured concentration value distribution is shown in table 11 below.
TABLE 11 determination of concentration value distribution
| Number of measurements | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 |
| 1 | 159.22 | 179.79 | 198.71 | 219.87 | 240.38 |
| 2 | 159.53 | 179.22 | 199.59 | 220.29 | 240.35 |
| 3 | 160.53 | 180.47 | 199.97 | 222.25 | 239.03 |
| 4 | 159.94 | 178.47 | 199.18 | 218.84 | 239.56 |
| 5 | 159.98 | 179.11 | 200.1 | 219.66 | 241.22 |
| 6 | 159.92 | 178.71 | 200.68 | 218.31 | 240.93 |
| 7 | 160.01 | 180.52 | 199.87 | 220.81 | 239.94 |
| 8 | 160.79 | 181.39 | 199.83 | 221.34 | 240.78 |
| 9 | 159.82 | 180.17 | 201.37 | 219.89 | 240.88 |
| 10 | 159.82 | 179.93 | 199.75 | 219.93 | 241.3 |
Based on the measurement results of table 11, linear and offset analyses were performed, and the obtained analysis report is shown in fig. 7.
As can be seen from fig. 7, the linearity value of the measurement method provided by the present invention=5.1% <10%; offset = 7.8% <10%, P = 0.75>0.05, meeting the requirements of the assay.
From the results of the embodiment 2, it can be seen that the determination method provided by the invention uses a spectrophotometry method of a quartz cuvette with characteristic wavelength of 800-900nm and optical path of 1mm, directly uses the working bath liquid to analyze the content of copper sulfate pentahydrate in the electroplating acidic copper plating liquid under the condition of not changing the property of the working bath liquid of the electroplating bath, and simultaneously, the stability of the whole measurement analysis system meets the requirements that GR & R is less than or equal to 10%, and the requirements that the linearity is less than 10%, the offset is less than 10% and the P is more than 0.05.
In summary, the invention provides a method for measuring the pentahydrate copper sulfate in the working bath solution of the electroplating bath, which can overcome the defects of the conventional EDTA titration method measurement analysis system, avoid the error caused by manually judging the titration end point by adopting EDTA for titration, improve the analysis precision and stability, avoid additional reagents and buffer solution, reduce the analysis cost and reduce the emission of ammonia nitrogen in wastewater. At the same time, compared with the spectrophotometry in the prior art, the method combines the color reagent with Cu 2+ Method for measuring concentration, which can avoid color former and Cu 2+ The reaction is incomplete or excessive, so that the measurement result is inaccurate, and the additional reagent and buffer solution are not needed, thereby reducing the analysis cost and reducing the emission of ammonia nitrogen in the wastewater.
In addition, the measuring method provided by the invention can directly analyze the content of the copper sulfate pentahydrate in the electroplating acidic copper plating solution by using the working solution under the condition of not changing the property of the working solution of the electroplating bath, is simple and quick, and the stability of the whole measuring and analyzing system meets the requirements of GR & R less than or equal to 10%, and the requirements of linearity less than 10%, offset less than 10% and P >0.05, so that the measuring method is a reliable analyzing method with practicability.
The above description is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention, and any changes and modifications made by those skilled in the art in light of the above disclosure are intended to fall within the scope of the appended claims. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The method for measuring the copper sulfate pentahydrate in the working bath solution of the electroplating bath is characterized by measuring the content of the copper sulfate pentahydrate in the working bath solution of the electroplating bath to be measured by adopting a spectrophotometer, wherein the content range of the copper sulfate pentahydrate in the working bath solution of the electroplating bath to be measured is 150-250g/L, and the characteristic wavelength adopted in the measurement by adopting the spectrophotometer is 800-900nm.
2. The method for measuring the copper sulfate pentahydrate in the working bath solution of the electroplating bath according to claim 1, wherein the cuvette used in the measurement by adopting a spectrophotometer is a quartz cuvette, and the optical path is 1mm.
3. The method for measuring copper sulfate pentahydrate in a working bath solution of an electroplating bath according to claim 1, wherein the measuring method specifically comprises the following steps:
s1: drawing a concentration-absorbance curve of a copper sulfate pentahydrate standard sample;
s2: taking working tank liquid of the plating tank to be measured into a cuvette of a spectrophotometer, and measuring absorbance of the working tank liquid of the plating tank to be measured by a machine;
s3: and obtaining the content of the copper sulfate pentahydrate in the working tank solution of the plating tank to be tested according to the concentration-absorbance curve and the absorbance of the working tank solution of the plating tank to be tested.
4. The method for measuring the copper sulfate pentahydrate in the working bath solution of the electroplating bath according to claim 1, wherein the content of the copper sulfate pentahydrate in the working bath solution of the electroplating bath to be measured is 180-220g/L.
5. The method for measuring the copper sulfate pentahydrate in the working bath solution of the electroplating bath according to claim 1, wherein the content of the copper sulfate pentahydrate in the working bath solution of the electroplating bath to be measured is 190-210g/L.
6. The method for measuring copper sulfate pentahydrate in the working bath solution of a plating tank according to claim 1, wherein the characteristic wavelength adopted in the measurement is 800-850nm.
7. The method for measuring copper sulfate pentahydrate in the working bath solution of a plating tank according to claim 1, wherein the characteristic wavelength adopted in the measurement is 800-820nm.
8. The method for measuring copper sulfate pentahydrate in the working bath solution of the electroplating bath according to claim 3, wherein the step S1 specifically comprises: and (3) obtaining the absorbance of at least 3 copper sulfate pentahydrate standard samples with different concentrations, then fitting a straight line by taking the concentration of the copper sulfate pentahydrate standard samples as an abscissa and the absorbance of the copper sulfate pentahydrate standard samples as an ordinate, and obtaining the concentration-absorbance curve.
9. The method for measuring copper sulfate pentahydrate in the working bath solution of the electroplating bath according to claim 3, wherein the step S1 specifically comprises: and (3) obtaining the absorbance of at least 5 copper sulfate pentahydrate standard samples with different concentrations, then fitting a straight line by taking the concentration of the copper sulfate pentahydrate standard samples as an abscissa and the absorbance of the copper sulfate pentahydrate standard samples as an ordinate, and obtaining the concentration-absorbance curve.
10. The method for measuring the copper sulfate pentahydrate in the working bath solution of the electroplating bath according to claim 8 or 9, wherein the standard copper sulfate pentahydrate sample comprises copper sulfate pentahydrate, sulfuric acid, chloride ions, a brightening agent, a carrier and a leveling agent.
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