CN114894878A - Method for measuring concentration of inhibitor in acidic copper plating solution - Google Patents
Method for measuring concentration of inhibitor in acidic copper plating solution Download PDFInfo
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- CN114894878A CN114894878A CN202210567839.8A CN202210567839A CN114894878A CN 114894878 A CN114894878 A CN 114894878A CN 202210567839 A CN202210567839 A CN 202210567839A CN 114894878 A CN114894878 A CN 114894878A
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Abstract
The invention discloses an analysis method for determining the concentration of an inhibitor in an acidic copper plating solution, which comprises the steps of carrying out voltammetry scanning by adopting a three-electrode system, carrying out differential calculation on a voltammetry curve to obtain a differential current and potential relation curve, and determining the concentration of the inhibitor in a plating solution sample to be determined according to the relation between the concentration of the inhibitor and the peak potential of the curve. The method of the invention is used for analyzing and detecting the concentration of the inhibitor in the acidic copper plating solution, and can eliminate the influence of other additives in the plating solution.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to an analysis method for determining the concentration of an inhibitor in an acidic copper plating solution.
Background
The inhibitor of the acidic copper plating solution is mainly water-soluble polyether polymer such as polyethylene glycol (PEG), polypropylene glycol (PPG) and copolymer thereof. Their inhibition capacity depends on the formation of a dense polymer network at the copper/electrolyte interface during copper deposition, which physically acts as a diffusion barrier, limiting the access of copper ions and other additives (e.g., accelerators) to the copper surface, and thus inhibiting it. An inappropriate suppressor concentration can lead to voids and seams in the via, and it is necessary to analyze the suppressor concentration in the plating solution in order to obtain a dense via fill.
US6899805 describes a method of inhibitor measurement, i.e. titration. When the system contains both the inhibitor and the accelerator, the accelerator needs to be diluted or saturated so as not to affect the determination of the inhibitor when the inhibitor is measured. Adding excessive promoter into the initial solution as base solution, performing cyclic voltammetry stripping scan on the initial solution to obtain peak area of the initial solution, and taking the peak area as AR 0 And continuously adding a standard solution into the system (only the inhibitor in the concentration of the system changes at the moment), and reducing the dissolution peak area ratio to obtain a standard curve. The ratio of the areas of the elution peaks of the plating liquid sample was measured in accordance with this method, and a titration curve of the plating liquid sample was obtained. Defining the inhibition factor as AR/AR 0 And calculating the equivalent inhibitor concentration in the plating solution to be tested under the preset inhibition factor. The method has the disadvantages that real-time online monitoring cannot be realized, the inhibition factor is introduced, and the calculation is complex. In order to reduce errors, multiple parallel experiments are needed for measuring the standard curve and the curve of the sample to be measured, the detection takes long time, the procedure is complicated, and the measurement has hysteresis.
CN201410447476 describes a method for determining the concentration of two inhibitors (accelerator and leveler) and setting the deposition rate ratio (Ri/R) 0 ) And the concentration ratio of the two inhibitors to the deposition rate is 0.75, calibration curves of the concentration ratio of the two inhibitors to the deposition rate are respectively drawn in two different potential ranges, and the first inhibition factor and the second inhibition factor are determined according to the concentration ratio of the accelerator standard solution to the leveling agent standard solution in the two potential ranges when the deposition rate ratio is 0.75. And (3) titrating the electroplating bath solution to be measured to obtain a curve of the deposition rate ratio and the additive dosage, and determining the equivalent inhibition concentration and the equivalent leveling agent concentration in two potential ranges respectively at the deposition rate ratio of 0.75. The method needs to draw a large amount of titration curves, and is complex to operate. In addition, the copper deposition rate is affected by various additives in the bath, and other additives (such as promoters) can have a large influence on the experimental results.
CN200710301372 describes a method for determining the concentration of an inhibitor or an accelerator from a plot of organic additive concentration versus peak potential for cyclic lift-off/cyclic pulse voltammetry. In actual production, the peak potential of the cyclic stripping method/cyclic pulse voltammetry stripping method is the comprehensive effect result of multiple additives in the plating solution, various additives of the copper plating solution fluctuate in the electroplating process, and when the promoter or inorganic additive chloride ions in the system change, the result is inaccurate when a single inhibitor is analyzed according to the peak potential of the cyclic stripping method/cyclic pulse voltammetry stripping method.
Disclosure of Invention
When the concentration of an inhibitor in a copper plating solution is measured by adopting a traditional cyclic voltammetry stripping method (CVS) or a cyclic pulse voltammetry stripping method (CPVS), the copper deposition rate is expressed according to the dissolution peak area (or dissolution peak electric quantity) of copper, the copper deposition rate is the result of the comprehensive action of an accelerator, an inhibitor, inorganic additives, chloride ions and the like in the plating solution, and when the concentration of other additives in the plating solution is changed, the copper deposition rate is also changed. The invention provides a method for monitoring the concentration of an inhibitor on line in real time by using a differential current-potential relation. The method is simple and rapid, has good stability, is not influenced by fluctuation of other additives in the plating solution, and can accurately determine the concentration of a single inhibitor. The determination of the working curve of the invention is based on the determination of the voltammetry curve after adding a minimum amount of inhibitor into the basic plating solution, and the potential at the maximum value of the differential current is obtained by selecting the deposition section of the voltammetry curve to conduct derivation on the current, which is defined as the DIV peak potential. The purpose of detecting the concentration of the inhibitor in the plating solution is achieved through the relationship between the concentration of the inhibitor and the DIV potential.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an analysis method for determining the concentration of an inhibitor in an acidic copper plating solution comprises the following steps:
(1) the basic plating solution comprises the following components: copper ions, sulfuric acid;
(2) drawing a detection standard curve: adding inhibitors with different concentrations into the basic plating solution, and performing voltammetry scanning by adopting an electrochemical three-electrode analysis method to obtain a current (I) -potential (U) voltammetry relation curve; and carrying out differential operation on the voltammetry curve to obtain a differential current and potential relation curve, namely a dI/dU-U curve (DIV for short). Drawing a relation standard curve of the concentration of the inhibitor and the DIV peak potential, and obtaining a standard curve fitting equation;
(3) sample detection: and adding the diluted plating solution to be measured into the basic plating solution, carrying out volt-ampere scanning to obtain DIV peak potential, substituting the DIV peak potential into a standard curve fitting equation, and calculating to obtain the concentration of the inhibitor in the plating solution sample to be measured.
Further, in step (2), the differential operation of the cyclic voltammogram includes, but is not limited to, a first derivative and a second derivative.
Further, in step (2), the fitting method of the working curve includes, but is not limited to, linear fitting and Langmuir fitting.
Further, in step (2), the DIV peak potential includes, but is not limited to, the potential at the maximum value of the differential current, and the potential at the minimum value of the differential current.
Further, the working electrode used by the three electrodes is a rotating disk electrode or a metal microelectrode, and the diameter range of the microelectrode is 1-500 μm. Working electrodes include, but are not limited to, gold, platinum, iridium, carbon fiber, glassy carbon, and the like.
Furthermore, the sweep rate of volt-ampere scanning is 0.01V/s-5V/s.
The method of the present invention is applicable to acidic copper plating systems containing similar additives but different anions, such as citrate ions, alkyl sulfonate ions, sulfamate ions, borate ions, etc., but also to the deposition of other metals such as zinc, tin, chromium, nickel, etc.
The invention has the beneficial effects that:
1. the method realizes the analysis and detection of the concentration of the inhibitor in the acidic copper plating solution, simultaneously eliminates the influence of other additives in the plating solution by adopting a dilution method (diluting by hundreds of times) to measure the concentration of the inhibitor in the plating solution, inspects the interference of the accelerator and the inorganic additive in a certain concentration range on the measurement of the inhibitor in the plating solution under the condition of diluting by 750 times, and has no interference as a result.
2. Because the dilution times can be conveniently and flexibly adjusted, the detection range of the concentration of the inhibitor is greatly increased.
3. The test accuracy is high, and the recovery rate of the four simulated plating solution samples is measured and is 93.0-100.6%.
4. Although the traditional titration method can also eliminate the influence of other additives, the experimental steps are complicated, the determination time is long, and the method provided by the invention does not need to determine a curve when determining the plating solution to be determined, thereby greatly shortening the analysis time and improving the analysis efficiency. The inhibitor in the plating solution can be supplemented and adjusted in time, so that the inhibitor is kept in a stable effective interval, the plating solution can be recycled, the electroplating cost is greatly reduced, and the chip defects can be reduced.
Drawings
FIG. 1 is a graph A showing a linear voltammogram in a copper plating solution; b represents a differential current-potential relation curve (DIV) obtained by performing differential processing on the linear voltammogram;
FIG. 2 is a linear voltammogram of the base bath to which a standard inhibitor was added as plotted in the working curve of example 1;
FIG. 3 is a graph of differential current versus potential (DIV) obtained by differentiating the linear voltammogram of FIG. 2;
FIG. 4 is a plot of inhibitor concentration versus DIV peak potential obtained when the working curve in example 1 was plotted;
FIG. 5 is an interference test for the determination of suppressor in base bath with varying accelerator (MPS) concentration; graph A is a linear voltammogram obtained by adding a promoter to a base plating solution containing a suppressor, and graph B is a differential current versus potential (DIV) corresponding to a differential treatment;
FIG. 6 is a graph of MPS concentration versus DIV peak potential;
FIG. 7 shows inorganic additives (Cl) – ) Interference tests for the determination of inhibitors in the base plating solution when the concentration is changed; graph A is a linear voltammetry curve of KCl added into a basic plating solution containing an inhibitor, and graph B is a corresponding differential current-potential relation curve (DIV) after differential treatment;
FIG. 8 is a graph of KCl concentration versus DIV peak potential.
The specific implementation mode is as follows:
the technical method in the embodiment of the invention is clearly and completely described below with reference to the attached drawings in the embodiment of the invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained according to the embodiments of the present invention by those skilled in the art without inventive labor fall within the scope of the present invention.
The invention provides an analysis method for determining the concentration of an inhibitor in an acidic copper plating solution, which comprises the following steps:
(1) the basic plating solution comprises the following components: copper ions, sulfuric acid;
(2) drawing a detection standard curve: adding inhibitors with different concentrations into the basic plating solution, and performing voltammetry scanning by adopting an electrochemical three-electrode analysis method; and carrying out differential operation on the voltammetry curve to obtain a DIV curve. Drawing a relation standard curve of the concentration of the inhibitor and the DIV peak potential, and obtaining a standard curve fitting equation;
(3) sample detection: and adding the diluted plating solution to be measured into the basic plating solution, carrying out volt-ampere scanning to obtain DIV peak potential, substituting the DIV peak potential into a standard curve fitting equation, and calculating to obtain the concentration of the inhibitor in the plating solution sample to be measured.
Example 1
Instruments and conditions:
the instrument comprises the following steps: electrochemical workstation, magnetic stirrers. A working electrode: 25um platinum microelectrode, reference electrode: Cu/CuSO 4 (saturated copper sulfate solution as internal filling liquid), counter electrode: a platinum electrode. Experiment temperature: and (4) room temperature.
And (3) an analysis step:
1. composition of the basic plating solution: 1M CuSO 4 +0.5M H 2 SO 4 +1.3333uM Cl - +0.0106ppm MPS
2. Preparing 4 simulated plating solution samples, wherein Bath = 1M CuSO 4 + 0.5 M H 2 SO 4 + 1 mM Cl – + 8 ppm MPS
Sample A to be tested: bath +300ppm PEG
Sample B to be tested: bath +270ppm PEG
Sample C to be tested: bath +210ppm PEG
Sample D to be tested: bath +150ppm PEG
3. Drawing a standard curve: continuously titrating and adding PEG with different concentrations into a beaker containing 10mL of basic plating solution, respectively measuring voltammetry curves when the concentration of the PEG is 0-1 ppm, performing differential treatment on the voltammetry curves under each concentration to obtain a differential current-potential relation curve (DIV), and drawing a relation graph between the concentration of the PEG and the DIV peak potential; a fit equation was obtained for PEG concentrations ranging from 0 to 0.5 ppm.
4. And (3) measuring the concentration of the inhibitor of the plating solution to be measured: and diluting the plating solution to be measured by 750 times, adding the diluted plating solution to the basic plating solution for voltammetry scanning, performing differential treatment to obtain a DIV peak potential, substituting the DIV peak potential into a working curve fitting equation to obtain the inhibitor concentration of the plating solution to be measured after the plating solution is diluted by 750 times, and finally obtaining the inhibitor concentration of the plating solution to be measured.
Example 2
The method provided by the invention is subjected to interference tests of other additive concentration changes, and the interference of the accelerator and the inorganic additive on the determination of the inhibitor is determined by adopting a same-rate dilution method. The formula of the acid copper plating solution mainly comprises CuSO 4 、H 2 SO 4 Inorganic additive (Cl) – ) An inhibitor (PEG), an accelerator (MPS). The same-rate dilution method refers to adding additive (Cl) in the plating solution – PEG and MPS) according to the concentration ratio and the same times, and the rest components in the plating solution are unchanged. The PEG concentration in the common plating solution formula is generally 300ppm, Cl – The concentration was 35.5 ppm, the MPS concentration was 8 ppm, where C PEG ：C MPS =37.5：1，C PEG ：C KCl = 8.45: 1. the base solution used for the interference performance experiment comprises the following components: 1M CuSO 4 + 0.5 M H 2 SO 4 + 0.4 ppm PEG, the MPS, KCl concentration range determined from the concentration ratio between PEG and MPS, KCl. The concentration of PEG in the base solution of the interference experiment is 0.4 ppm, the concentration range of MPS in the interference experiment is set to be 0-0.02 ppm according to the concentration ratio of PEG to MPS, and the concentration range of KCl in the interference experiment is set to be 0-5 mu M KCl. Within this concentration range, as shown in fig. 6: it was found that when the concentration of MPS was varied,the mean value of DIV peak potential measurement is-0.268V, and RSD is within 2.5%, which indicates that MPS has no interference to the measurement of PEG concentration in the base solution. As shown in fig. 8: when the KCl concentration is changed, the average value of DIV peak potential measurement is-0.266V, and RSD is within 2.0 percent, which indicates that KCl has no interference on the measurement of PEG concentration in the base solution.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A method for determining the concentration of an inhibitor in an acidic copper plating solution is characterized in that: the method comprises the following steps:
(1) the basic plating solution comprises the following components: copper ions, sulfuric acid;
(2) drawing a detection standard curve: adding inhibitors with different concentrations into the basic plating solution, and performing voltammetry scanning by adopting an electrochemical three-electrode analysis method to obtain a current (I) -potential (U) voltammetry relation curve; carrying out differential operation on the volt-ampere curve to obtain a differential current and potential relation curve, namely a dI/dU-U curve (DIV for short); drawing a relation standard curve of the concentration of the inhibitor and the DIV peak potential, and obtaining a standard curve fitting equation;
(3) sample detection: and adding the diluted plating solution to be measured into the basic plating solution, carrying out volt-ampere scanning to obtain DIV peak potential, substituting the DIV peak potential into a standard curve fitting equation, and calculating to obtain the concentration of the inhibitor in the plating solution sample to be measured.
2. The method of determining the concentration of an inhibitor in an acidic copper plating bath according to claim 1, wherein: the differential operation of the voltammogram includes, but is not limited to, first derivative, second derivative.
3. The method of determining the concentration of an inhibitor in an acidic copper plating bath according to claim 1, wherein: the fitting method of the working curve includes, but is not limited to, linear fitting, Langmuir fitting.
4. The method of determining the concentration of an inhibitor in an acidic copper plating bath according to claim 1, wherein: the DIV peak potential includes, but is not limited to, the potential at the maximum of the differential current, the potential at the minimum of the differential current.
5. The method for determining the concentration of an inhibitor in an acidic copper plating solution according to claim 1, wherein: the working electrode used by the three electrodes is a rotating disk electrode or a metal microelectrode, the diameter range of the microelectrode is 1-500 mu m, and the working electrode material comprises but is not limited to gold, platinum, iridium, carbon fiber and glassy carbon.
6. The method of determining the concentration of an inhibitor in an acidic copper plating bath according to claim 1, wherein: electrochemical analytical methods including, but not limited to, linear voltammetry, cyclic voltammetry stripping, cyclic pulse voltammetry stripping, square wave voltammetry, differential pulse voltammetry.
7. The method of determining the concentration of an inhibitor in an acidic copper plating bath according to claim 1, wherein: the sweep rate range of volt-ampere scanning is 0.01V/s-5V/s.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029886A (en) * | 2007-03-29 | 2007-09-05 | 上海大学 | Method for determining nitrobenzyl phenol three isomer simultaneouslly |
| CN101320015A (en) * | 2008-07-21 | 2008-12-10 | 中国农业大学 | Method for fast detecting vitamin E content |
| US20090057151A1 (en) * | 2007-08-27 | 2009-03-05 | Eci Technology, Inc. | Detection of additive breakdown products in acid copper plating baths |
| CN101470097A (en) * | 2007-12-25 | 2009-07-01 | 比亚迪股份有限公司 | Measuring method for concentration of organic additive in plating solution |
| RU2484455C1 (en) * | 2011-12-13 | 2013-06-10 | Федеральное Государственное Автономное Образовательное Учреждение Высшего Профессионального Образования "Сибирский Федеральный Университет" | Method for stripping voltametric determination of platinum in nitrite medium |
| US20170219542A1 (en) * | 2016-02-03 | 2017-08-03 | Shimadzu Corporation | Peak extraction method and program |
| CN110412102A (en) * | 2019-06-19 | 2019-11-05 | 天津力神电池股份有限公司 | The measuring method of additive level in a kind of lithium-ion battery electrolytes |
| CN111650264A (en) * | 2020-03-30 | 2020-09-11 | 广州钰芯传感科技有限公司 | Method for detecting artificially synthesized pigment by derivative voltammetry |
| CN112326872A (en) * | 2020-11-04 | 2021-02-05 | 中国航发哈尔滨轴承有限公司 | Method for detecting concentration of magnesium sulfate and nickel sulfate in multi-component mixed nickel electroplating solution |
| CN113237938A (en) * | 2021-05-10 | 2021-08-10 | 深圳市朗石科学仪器有限公司 | Method for detecting heavy metals in surface water based on second-order differential peak finding method |
-
2022
- 2022-05-24 CN CN202210567839.8A patent/CN114894878A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029886A (en) * | 2007-03-29 | 2007-09-05 | 上海大学 | Method for determining nitrobenzyl phenol three isomer simultaneouslly |
| US20090057151A1 (en) * | 2007-08-27 | 2009-03-05 | Eci Technology, Inc. | Detection of additive breakdown products in acid copper plating baths |
| CN101470097A (en) * | 2007-12-25 | 2009-07-01 | 比亚迪股份有限公司 | Measuring method for concentration of organic additive in plating solution |
| CN101320015A (en) * | 2008-07-21 | 2008-12-10 | 中国农业大学 | Method for fast detecting vitamin E content |
| RU2484455C1 (en) * | 2011-12-13 | 2013-06-10 | Федеральное Государственное Автономное Образовательное Учреждение Высшего Профессионального Образования "Сибирский Федеральный Университет" | Method for stripping voltametric determination of platinum in nitrite medium |
| US20170219542A1 (en) * | 2016-02-03 | 2017-08-03 | Shimadzu Corporation | Peak extraction method and program |
| CN110412102A (en) * | 2019-06-19 | 2019-11-05 | 天津力神电池股份有限公司 | The measuring method of additive level in a kind of lithium-ion battery electrolytes |
| CN111650264A (en) * | 2020-03-30 | 2020-09-11 | 广州钰芯传感科技有限公司 | Method for detecting artificially synthesized pigment by derivative voltammetry |
| CN112326872A (en) * | 2020-11-04 | 2021-02-05 | 中国航发哈尔滨轴承有限公司 | Method for detecting concentration of magnesium sulfate and nickel sulfate in multi-component mixed nickel electroplating solution |
| CN113237938A (en) * | 2021-05-10 | 2021-08-10 | 深圳市朗石科学仪器有限公司 | Method for detecting heavy metals in surface water based on second-order differential peak finding method |
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