CN116297782A - Method, device, equipment and medium for measuring concentration of additive in acidic copper plating solution based on ultramicro electrode - Google Patents
Method, device, equipment and medium for measuring concentration of additive in acidic copper plating solution based on ultramicro electrode Download PDFInfo
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- 238000005259 measurement Methods 0.000 abstract description 7
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Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
Abstract
The invention relates to the technical field of electrochemical analysis, in particular to a method, a device, equipment and a medium for measuring the concentration of an additive in an acidic copper plating solution based on an ultramicro electrode. According to the determination method provided by the invention, a three-electrode system with the ultramicro electrode as a working electrode is adopted for cyclic voltammetry scanning, and the accurate determination of the concentrations of the accelerator, the leveler and the inhibitor in the plating solution sample to be detected is realized according to the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the additive and the accurate regulation and control of the influencing factors. The method can be used for measuring the concentrations of the accelerator, the leveling agent and the inhibitor in the acidic copper plating solution, ignoring the interference of other two additives on the concentration measurement, and realizing the rapid detection of the three additives.
Description
Technical Field
The invention relates to the technical field of electrochemical analysis, in particular to a method, a device, equipment and a medium for measuring the concentration of an additive in an acidic copper plating solution based on an ultramicro electrode.
Background
The update iteration of electronic products is independent of the support and development of electronic circuit manufacturing technology. Electronic copper plating is one of the core technologies in the field of electronic circuit fabrication, such as printed circuit boards (Printed Circuit Board, PCB), through silicon vias (Through Silicon Via, TSVs), and damascene chips.
The electronic copper plating mainly adopts acidic copper sulfate plating solution. The acidic copper plating solution is depleted of copper sulfate, sulfuric acid and Cl - In addition, three types of functional organic additives are included: inhibitors, accelerators, and levelers. The inhibitor is usually an organic polymer such as polyethylene glycol (PEG), polypropylene glycol (PPG), and ethylene oxide propylene oxide block copolymer (EOPO), etc., and is used for blocking Cu by forming an inhibitor-Cl-blocking layer on the surface of Cu 2+ Ions enter the Cu surface, reducing the copper ion deposition rate. Accelerators such as sodium polydithio-dipropyl sulfonate (SPS) and 3-mercapto-1-propane sulfonic acid (MPS) are adsorbed on the cathode surface through mercapto groups, and the sulfonic acid group on the other side attracts and captures copper ions to the cathode surface by electrostatic action, thereby improving the copper ion deposition rate. The leveling agent is usually nitrogen-containing heterocyclic compound or quaternary ammonium salt, and common leveling agents are benalagreen (JGB), gentian violet, diazine Black (DB), 2-mercaptopyridine (2-MP), etc. The leveling agent molecules are usually provided with one or more positive charges, are more easily adsorbed in the high current density area, inhibit copper ions in the high current density area from being reduced, and achieve the effect of leveling the protruding parts of the side walls or blind holes of the micro-through holes. In the actual electroplating process, the concentration of the additive in the plating solution changes due to factors such as carrying out and decomposition of the plating piece, so that the plating solution changes, and the product yield is affected. Thus detectingThe concentration of the organic additive in the acidic copper plating solution is very necessary.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method, a device, equipment and a medium for measuring the concentration of an additive in an acidic copper plating solution based on an ultramicro electrode.
In order to solve the technical problems, one of the technical schemes provided by the invention is as follows:
a method for determining the concentration of an additive in an acidic copper plating solution based on an ultra-microelectrode, wherein the additive mainly comprises an inhibitor, an accelerator and a leveling agent, and the method comprises the following steps:
measuring the concentration of the inhibitor, namely diluting a plating solution sample to reduce the influence of an accelerator and a leveling agent in the plating solution sample, and obtaining the concentration of the inhibitor according to the corresponding relation between the dissolved electric quantity of a deposited copper anode and the concentration of the inhibitor;
measuring the concentration of the accelerator, namely adjusting the concentration of the inhibitor and the leveling agent in the plating solution sample to be saturated adsorption concentration, and obtaining the concentration of the accelerator according to the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the accelerator;
and measuring the concentration of the leveling agent, namely preparing electroplating solutions with different concentrations of the leveling agent through known inhibitor concentration and accelerator concentration, and obtaining the concentration of the leveling agent through the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the leveling agent.
In a more preferred embodiment, the determination of the inhibitor concentration comprises the steps of:
(1) Preparing electroplating stock solution, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test to measure the stripping electric quantity Q of the deposited copper anode VMS ；
(2) Adding an inhibitor into the electroplating stock solution to form a standard solution A with known inhibitor concentration;
(3) Mixing the standard solution A with the electroplating stock solution according to a certain volume ratio to obtain standard solution B with different known inhibitor concentrations, and performing a stripping voltammetry test by adopting a three-electrode system with an ultramicro electrode as a working electrode to obtain a deposited copper anodePolar dissolved electric quantity ratio Q/Q VMS Wherein Q and Q VMS Respectively dissolving out electric quantity of the deposited copper anode containing the inhibitor and the deposited copper anode without the inhibitor;
(4) According to the ratio Q/Q of the dissolved electric quantity of the anode of the deposited copper VMS Drawing a standard concentration curve of the inhibitor according to the corresponding relation between the inhibitor concentration and the inhibitor concentration;
(5) Mixing a plating solution sample with an electroplating stock solution according to a certain volume ratio, and measuring the ratio Q of the dissolved electric quantity of a deposited copper anode of the diluted plating solution sample Sample of /Q VMS Will Q Sample of /Q VMS Comparing with the inhibitor concentration standard curve, wherein the corresponding abscissa value is the inhibitor concentration value in the diluted plating solution sample; and calculating the concentration of the inhibitor in the plating solution sample according to the dilution ratio of the plating solution sample.
In a more preferred embodiment, the plating solution sample is mixed with the plating stock solution in a volume ratio of (1:50) - (1:1000).
In a more preferred embodiment, the determination of the accelerator concentration comprises the steps of:
(1) Adding an inhibitor and a leveling agent with saturated adsorption concentration into electroplating stock solution to obtain a mixed solution A, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test to measure the stripping electric quantity Q of a deposited copper anode 0 ；
(2) Mixing a plating solution sample with the mixed solution A according to a certain volume ratio to obtain a mixed solution B, performing CVS test by adopting a three-electrode system with an ultramicro electrode as a working electrode, and measuring the dissolved electric quantity ratio Q of a deposited copper anode 1 /Q 0 Wherein Q is 1 And Q 0 The dissolved electric quantity of the deposited copper anode containing the accelerator and the deposited copper anode without the accelerator respectively;
(3) Taking i parts of mixed solution B, respectively adding known accelerators with different volumes into the mixed solution B to form a standard solution i, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test to obtain a stripping electric quantity ratio Q of a deposited copper anode 2 /Q 0 ，Q 3 /Q 0 ,......Q i /Q 0 ；
(4) According to the steps (2) and (3), the ratio of the dissolved electric quantity is taken as an ordinate and the concentration of the accelerator is taken as an abscissa, a fitting straight line is formed by the measured ratio of the dissolved electric quantity and the concentration of the accelerator, and the fitting straight line and the straight line y=q are obtained through drawing 0 And (3) obtaining the accelerator concentration of the plating solution sample according to the dilution ratio of the step (2) by the abscissa value of the intersection point.
In a more preferred embodiment, the volume ratio of the plating solution sample to the mixed solution A is (1:1) - (1:50).
In a more preferred embodiment, the determination of leveler concentration comprises the steps of:
(1) Adding inhibitor and accelerator into electroplating stock solution to the same concentration as the inhibitor and accelerator in the plating solution sample to form standard solution C, and measuring the stripping electric quantity Q of the deposited copper anode by using a three-electrode system with an ultramicro electrode as a working electrode to carry out stripping voltammetry test 0 ’；
(2) Adding a leveling agent into the standard solution C to form a standard solution D with known leveling agent concentration;
(3) Mixing the standard solution C and the standard solution D according to a certain volume ratio to obtain solutions with different known leveling agent concentrations, adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test, and drawing the stripping electric quantity ratio Q'/Q of different deposited copper anodes 0 'wherein Q' and Q 0 ' the dissolved power of the deposited copper anode with and without the leveling agent, respectively;
(4) According to the ratio Q'/Q of the dissolved electric quantity of the anode of the deposited copper 0 ' corresponding relation with leveling agent concentration, drawing a leveling agent standard concentration curve;
(5) The three-electrode system with the ultramicro electrode as the working electrode is adopted to test the plating solution sample by a stripping voltammetry method, and the stripping electric quantity ratio Q of the deposited copper anode of the plating solution sample is measured Sample of ’/Q 0 ' will Q Sample of ’/Q 0 And comparing the' with a standard concentration curve of the leveling agent, wherein the corresponding abscissa value is the concentration of the leveling agent in the sample liquid to be measured.
In a more preferred embodiment, the volume ratio of the standard solution A to the standard solution B is (1:1) - (1:100).
The second technical scheme provided by the invention is as follows:
a detection device for determining the concentration of an additive in an acidic copper plating solution based on an ultramicro electrode, wherein the additive mainly comprises an inhibitor, an accelerator and a leveling agent, and the detection device comprises the following components:
the inhibitor concentration measuring module is used for diluting the plating solution sample to reduce the influence of an accelerator and a leveling agent in the plating solution sample, and obtaining the concentration of the inhibitor according to the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the inhibitor;
the accelerator concentration measuring module is used for adjusting the concentration of the inhibitor and the leveling agent in the plating solution sample to the saturated adsorption concentration, and obtaining the concentration of the accelerator according to the corresponding relation between the dissolved electric quantity of the deposited copper anode and the accelerator concentration;
and the leveling agent concentration measuring module is used for preparing electroplating solutions with different leveling agent concentrations through known inhibitor concentrations and accelerator concentrations, and obtaining the concentration of the leveling agent through the corresponding relation between the dissolved electric quantity of the deposited copper anode and the leveling agent concentration.
The third technical scheme provided by the invention is as follows:
a computer device comprising a memory, a processor and a computer program stored in the memory and executable on the processor, when executing the computer program, implementing a method for determining the concentration of an additive in an acidic copper plating solution based on an ultra-microelectrode as described above.
The technical scheme provided by the invention is as follows:
a computer-readable storage medium storing a computer program, characterized in that: the computer program when executed by the processor implements the method for determining the concentration of the additive in the acidic copper plating solution based on the ultramicroelectrode as described above.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the method is suitable for monitoring the concentration of the acid copper plating additive in real time in the electroplating production line.
The technical scheme provided by the invention can realize the accurate detection of the concentration of the inhibitor, the accelerator and the leveling agent in the plating liquid system, and when the concentration of a single additive is measured, the interference of other two additives in the plating liquid can be greatly reduced by adopting the method, so that the method is suitable for monitoring the concentration of the additive of the plating liquid on the electroplating production line.
2. The method for determining the concentration of the additive is simple and quick.
Aiming at the concentration detection of the inhibitor, only one standard curve of the concentration of the inhibitor is drawn, and the method can be continuously used under the same working condition, has short measurement time and has a standard error within a range of 5 percent.
Aiming at the accelerator concentration detection, the accelerator concentration in the plating solution sample can be obtained by drawing a fitting straight line only by carrying out 6-8 times of stripping voltammetry scanning without drawing a concentration curve, and the error is within a range of 5%;
for leveling agent concentration determination, the accelerator and inhibitor detection method provided by the invention can be combined to achieve rapid determination, and the method can also only involve drawing of one leveling agent concentration standard curve, and the error is within a range of 5%.
3. The measuring device is simple and convenient.
The microelectrode adopted by the invention is used for measuring the concentration of three organic additives in a plating liquid system, and compared with the traditional rotating disk electrode, the method has the advantages of small liquid consumption, small ohmic pressure drop and the like.
4. Is convenient for development and application.
The three-electrode system in the method can be applied to a microfluidic device, so that the plating solution amount required by plating solution analysis is greatly reduced, the power consumption is low, and the device cost is low, thereby achieving the purposes of energy conservation, environmental protection and cost saving.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
For a clearer description of embodiments of the invention or of the solutions of the prior art, the drawings that are needed in the description of the embodiments or of the prior art will be briefly described, it being obvious that the drawings in the description below are some embodiments of the invention, and that other drawings can be obtained from them without inventive effort for a person skilled in the art; the positional relationships described in the drawings in the following description are based on the orientation of the elements shown in the drawings unless otherwise specified.
FIG. 1 is a schematic flow chart of a method for determining the concentration of an additive in an acidic copper plating solution based on an ultra-microelectrode;
FIG. 2 is a plot of stripping voltammograms for different inhibitor concentrations;
FIG. 3 is a graph of the ratio of the dissolved electricity of a deposited copper anode versus the concentration of inhibitor;
FIG. 4 is a plot of stripping voltammograms of a plating solution sample versus a diluted plating solution sample;
FIG. 5 is a graph of the ratio of the dissolved electrical energy of a deposited copper anode for a diluted plating solution sample, corresponding to the ratio of the dissolved electrical energy of the deposited copper anode versus the concentration of the inhibitor;
FIG. 6 is a plot of stripping voltammograms from a plating bath containing inhibitors and accelerators at saturated adsorption concentrations mixed in a ratio with a sample of the bath with different concentrations of accelerator added;
FIG. 7 is a graph of a fit for calculating the accelerator concentration in a plating solution sample, with the absolute value of the abscissa being the accelerator concentration in the plating solution sample;
FIG. 8 is a standard graph of leveler addition at different concentrations to leveler blank Solutions (LFEs) containing the same inhibitor and accelerator concentrations as the plating bath samples;
FIG. 9 is a graph of the ratio of dissolved charge of leveler versus leveler concentration for the addition of different concentrations of leveler to a leveler blank solution (LFE) containing the same inhibitor and accelerator concentrations as the plating bath sample;
FIG. 10 is a plot of stripping voltammograms for plating solution sample one and plating solution sample two;
FIG. 11 is a graph of the amount of dissolved electricity of a plating bath sample versus leveler standard concentration;
FIG. 12 is a schematic structural view of a detecting device for measuring the concentration of an additive in an acidic copper plating solution based on an ultramicroelectrode;
FIG. 13 is a schematic structural view of a detecting device for measuring the concentration of an additive in an acidic copper plating solution based on an ultra-micro electrode according to another embodiment of the present invention;
fig. 14 is a schematic structural diagram of a computer device according to the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention provides a method for measuring the concentration of an inhibitor, an accelerator and a leveling agent in acid copper plating solution based on an ultramicro electrode three-electrode system according to the corresponding relation between the dissolved electric quantity of a deposited copper anode and the concentration of three additives in the plating solution and the accurate regulation and control of influencing factors. The ultra-microelectrode has a very thin diffusion layer thickness and can obtain the kinetic parameters of electrochemical intrinsic reaction relatively quickly. The three-electrode system using the ultramicro electrode as the working electrode can be used for carrying out electrochemical analysis on the solution rapidly with low cost; the electrochemical analysis is carried out by combining a cyclic voltammetry, according to the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the additive, the concentration of the inhibitor, the accelerator and the leveling agent in the plating solution sample can be measured, the influence of other additives can be ignored to a certain extent, and the influence of other additives is removed by combining a saturated adsorption concentration and a dilution mode, so that a more accurate concentration measurement value is obtained.
An embodiment of the present invention provides a method for determining the concentration of an additive in an acidic copper plating solution based on an ultra-micro electrode, the additive consisting essentially of an inhibitor, an accelerator, and a leveler, comprising:
and 3, measuring the concentration of the leveling agent, namely preparing electroplating solutions with different concentrations of the leveling agent through known inhibitor concentration and accelerator concentration, and obtaining the concentration of the leveling agent through the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the leveling agent.
It should be noted that, in the description of the present embodiment, the continuous reference numerals of the method steps are used for facilitating examination and understanding, and by combining the overall technical scheme of the present embodiment and the logic relationships between the steps, the implementation sequence between the partial steps is adjusted without affecting the technical effect achieved by the technical scheme of the present embodiment. The contents of each step are discussed in detail below:
in one embodiment, the determination of the inhibitor concentration comprises the steps of:
(1) Preparing electroplating stock solution (VMS), and performing stripping voltammetry test by adopting a three-electrode system with an ultramicro electrode as a working electrode to obtain the stripping electric quantity Q of the deposited copper anode VMS ；
(2) Adding an inhibitor into the electroplating stock solution to form a standard solution A with known inhibitor concentration;
(3) Mixing the standard solution A with the electroplating stock solution according to a certain volume ratio to obtain standard solution B with different known inhibitor concentrations, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry (CVS) test to measure the stripping electric quantity ratio Q/Q of the deposited copper anode VMS Wherein Q and Q VMS Respectively dissolving out electric quantity of the deposited copper anode containing the inhibitor and the deposited copper anode without the inhibitor;
(4) According to the ratio Q/Q of the dissolved electric quantity of the anode of the deposited copper VMS Drawing a standard concentration curve of the inhibitor according to the corresponding relation between the inhibitor concentration and the inhibitor concentration;
(5) Mixing a plating solution sample with an electroplating stock solution according to a certain volume ratio, and measuring the ratio Q of the dissolved electric quantity of a deposited copper anode of the diluted plating solution sample Sample of /Q VMS Will Q Sample of /Q VMS Comparing with the inhibitor concentration standard curve, wherein the corresponding abscissa value is the inhibitor concentration value in the diluted plating solution sample; according to the dilution ratio of the plating solution sample, calculating the concentration of the inhibitor in the plating solution sample;
preferably, the volume ratio of the plating solution sample to the plating stock solution is (1:50) - (1:1000).
In one embodiment, the determination of the accelerator concentration comprises the steps of:
(1) Adding 100-1000 ppm inhibitor and 10-100 ppm leveling agent to obtain mixed solution A, and measuring with three-electrode system with ultramicro electrode as working electrode to obtain deposited copper anodeDissolved electric quantity Q 0 ；
(2) Mixing a plating solution sample with the mixed solution A according to a certain volume ratio to obtain a mixed solution B, performing CVS test by adopting a three-electrode system with an ultramicro electrode as a working electrode, and measuring the dissolved electric quantity ratio Q of a deposited copper anode 1 /Q 0 Wherein Q is 1 And Q 0 The dissolved electric quantity of the deposited copper anode containing the accelerator and the deposited copper anode without the accelerator respectively;
preferably, the volume ratio of the plating solution sample to the mixed solution A is (1:1) - (1:50).
(3) Taking i parts of mixed solution B, respectively adding known accelerators with different volumes into the mixed solution B to form a standard solution i, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test to obtain a stripping electric quantity ratio Q of a deposited copper anode 2 /Q 0 ，Q 3 /Q 0 ,......Q i /Q 0 ；
(4) According to the steps (2) and (3), the ratio of the dissolved electric quantity is taken as an ordinate and the concentration of the accelerator is taken as an abscissa, a fitting straight line is formed by the measured ratio of the dissolved electric quantity and the concentration of the accelerator, and the fitting straight line and the straight line y=q are obtained through drawing 0 And (3) obtaining the accelerator concentration of the plating solution sample according to the dilution ratio of the step (2) by the abscissa value of the intersection point.
In one embodiment, the determination of leveler concentration includes the steps of:
(1) Adding inhibitor and accelerator into electroplating stock solution to the same concentration as the inhibitor and accelerator in the plating solution sample to form standard solution C, and measuring the stripping electric quantity Q of the deposited copper anode by using a three-electrode system with an ultramicro electrode as a working electrode to carry out stripping voltammetry test 0 ’；
(2) Adding a leveling agent into the standard solution C to form a standard solution D with known leveling agent concentration;
(3) Mixing the standard solution C and the standard solution D according to a certain volume ratio to obtain solutions with different known leveling agent concentrations, and performing stripping voltammetry measurement by adopting a three-electrode system with an ultramicro electrode as a working electrodeTesting, drawing the ratio Q'/Q of the dissolved electric quantity of different deposition copper anodes 0 'wherein Q' and Q 0 ' the dissolved power of the deposited copper anode with and without the leveling agent, respectively;
preferably, the volume ratio of the standard solution C to the standard solution D is (1:1) - (1:100);
(4) According to the ratio Q'/Q of the dissolved electric quantity of the anode of the deposited copper 0 ' corresponding relation with leveling agent concentration, drawing a leveling agent standard concentration curve;
(5) The three-electrode system with the ultramicro electrode as the working electrode is adopted to test the plating solution sample by a stripping voltammetry method, and the stripping electric quantity ratio Q of the deposited copper anode of the plating solution sample is measured Sample of ’/Q 0 ' will Q Sample of ’/Q 0 And comparing the' with a standard concentration curve of the leveling agent, wherein the corresponding abscissa value is the concentration of the leveling agent in the sample liquid to be measured.
In a preferred embodiment, the microelectrodes include, but are not limited to, platinum and silver electrodes, with diameters ranging from 1 μm to 50 μm.
In a preferred embodiment, the electrochemical test potential scan is in the range of-0.8V or more and 1.5V or less.
Among them, inhibitors include, but are not limited to, polyethylene glycol, ethylene oxide propylene oxide block copolymers, polypropylene glycol, and the like; accelerators include, but are not limited to, sodium polydithio-dipropyl sulfonate, 3-mercapto-1-propane sulfonic acid, and the like; leveling agents include, but are not limited to, nitrogen-containing heterocyclic compounds or quaternary ammonium salts such as benalachlor, gentian violet, diazine black, and 2-mercaptopyridine.
The technical scheme of the present invention is further illustrated and described below by specific examples, but the scope of the present invention is not limited thereto.
Example 1
Referring to FIGS. 1 to 5, the concentration of the inhibitor in the acidic copper plating solution was measured in this example;
experimental instrument and experimental conditions:
experimental instrument: electrochemical workstation CHI760E, magnetic stirrer, ultrasonic cleaner.
Working electrode: a 25 μm platinum microelectrode; a reference electrode: a mercurous sulfate electrode; auxiliary electrode:
platinum sheet electrodes.
Experimental conditions: room temperature
The analysis step:
In this example 1, the plating stock solution was prepared as follows: 75g/L CuSO 4 ·5H 2 O,180g/L H 2 SO 4 60mg/L NaCl;
in this example 1, inhibitor concentration measurements were performed on a configured plating solution sample containing the following components: 75g/L CuSO 4 ·5H 2 O,180g/L H 2 SO 4 60mg/L NaCl,300mg/L inhibitor PEG (molecular weight 8000), 1mg/L accelerator SPS,3mg/L leveler JGB;
and 5, calculating the corresponding relation curve of the dissolved electric quantity ratio of the diluted plating solution sample to the concentration of the inhibitor corresponding to the dissolved electric quantity ratio of the deposited copper anode, wherein the concentration of the inhibitor in the plating solution sample is calculated to be 6.05 mg/L), and the experimental error of the example is 0.8%.
Further, please refer to fig. 1 and fig. 6-7, the accelerator concentration in the plating solution is measured;
experimental instrument and experimental conditions:
experimental instrument: electrochemical workstation CHI760E, magnetic stirrer, ultrasonic cleaner.
Working electrode: a 25 μm platinum microelectrode; a reference electrode: a mercurous sulfate electrode; auxiliary electrode: platinum sheet electrodes.
Experimental conditions: room temperature
The analysis step:
In this example 1, the plating stock solution was prepared as follows: 75g/L CuSO 4 ·5H 2 O,180g/L H 2 SO 4 60mg/L NaCl;
in this example 1, accelerator concentration measurements were performed on a plating solution sample containing the following components: 75g/L CuSO 4 ·5H 2 O,180g/L H 2 SO 4 60mg/L NaCl,300mg/L inhibitor PEG (molecular weight 8000), 1mg/L accelerator SPS,3mg/L leveler JGB;
and 6, fitting a straight line, wherein the absolute value of the abscissa of the straight line is multiplied by the dilution factor to obtain the accelerator concentration (0.955 ppm) in the plating solution sample, and the experimental error of the example is 4.5%.
Further, referring to fig. 1 and 8-11, the concentration of leveler in the plating solution is measured;
experimental instrument and experimental conditions:
experimental instrument: electrochemical workstation CHI760E, magnetic stirrer, ultrasonic cleaner.
Working electrode: a 25 μm platinum microelectrode; a reference electrode: a mercurous sulfate electrode; auxiliary electrode: platinum sheet electrodes.
Experimental conditions: room temperature
The analysis step:
In this example 1, the plating stock solution was prepared as follows: 75g/L CuSO 4 ·5H 2 O,180g/L H 2 SO 4 60mg/L NaCl;
in this example 1, leveling agent concentration measurement was performed by preparing a first plating solution sample and a second plating solution sample containing the following components, wherein the inhibitor concentration and the accelerator concentration in the first plating solution sample and the second plating solution sample were measured by the methods described above and are known:
composition of plating solution sample one: 75g/L CuSO 4 ·5H 2 O,180g/L H 2 SO 4 60mg/L NaCl,300mg/L inhibitor PEG (molecular weight 8000), 1mg/L accelerator SPS,2.5mg/L leveler JGB;
composition of plating solution sample two: 75g/L CuSO 4 ·5H 2 O,180g/L H 2 SO 4 60mg/L NaCl,300mg/L inhibitor PEG (molecular weight 8000), 1mg/L accelerator SPS,3.5mg/L leveler JGB;
and 5, calculating the JGB concentration (2.54 ppm and 3.46 ppm) in the plating solution sample by using a corresponding relation curve of the dissolved electric quantity ratio of the diluted plating solution sample to the concentration of the leveling agent, wherein the average experimental error of the sample is 1.3%.
The above embodiments provide methods for measuring the inhibitor, the accelerator and the leveler respectively, and the leveling agent concentration of the plating solution sample is measured by the method formed by the method and the method for measuring the three additives more quickly and accurately.
Example 2
Referring to fig. 12 and 13, there is provided a detection device for determining the concentration of an additive in an acidic copper plating solution based on an ultra-micro electrode, wherein the additive is mainly composed of an inhibitor, an accelerator and a leveler, and comprises:
the inhibitor concentration determination module 10 is configured to dilute the plating solution sample to reduce the influence of the accelerator and the leveler in the plating solution sample, and obtain the inhibitor concentration from the corresponding relationship between the dissolved electric quantity of the deposited copper anode and the inhibitor concentration;
the accelerator concentration measuring module 20 is configured to obtain the accelerator concentration by adjusting the concentration of the inhibitor and the leveler in the plating solution sample to a saturated adsorption concentration and then obtaining the accelerator concentration from the corresponding relationship between the dissolved electric quantity of the deposited copper anode and the accelerator concentration;
the leveler concentration measuring module 30 is configured to prepare electroplating solutions with different leveler concentrations through known inhibitor concentrations and accelerator concentrations, and obtain the leveler concentration from the corresponding relationship between the dissolved electric quantity of the deposited copper anode and the leveler concentration.
Example 3
Referring to fig. 14, the present invention provides a computer device, including a memory, a processor, and a computer program stored in the memory and capable of running on the processor, where the processor implements the method for determining the concentration of an additive in an acidic copper plating solution based on an ultramicroelectrode in the above embodiment when executing the computer program, for example, the steps shown in fig. 1 are omitted herein for avoiding repetition. Alternatively, the processor, when executing a computer program, implements the functions of each module/unit of the detection device for measuring the concentration of the additive in the acidic copper plating solution based on the microelectrode in the above-described embodiment, such as the functions of the modules 10 to 30 shown in fig. 12. In order to avoid repetition, a description thereof is omitted.
Example 4
In an embodiment, the present invention provides a computer readable storage medium, where a computer program is stored, where the computer program when executed by a processor implements the method for determining the concentration of an additive in an acidic copper plating solution based on an ultramicroelectrode in the above embodiment, for example, the steps shown in fig. 1, and for avoiding repetition, a description is omitted here. Alternatively, the processor, when executing a computer program, implements the functions of each module/unit of the detection device for measuring the concentration of the additive in the acidic copper plating solution based on the microelectrode in the above-described embodiment, such as the functions of the modules 10 to 30 shown in fig. 12. In order to avoid repetition, a description thereof is omitted.
Those skilled in the art will appreciate that implementing all or part of the above described methods may be accomplished by way of a computer program stored on a non-transitory computer readable storage medium, which when executed, may comprise the steps of the embodiments of the methods described above. Any reference to memory, storage, database, or other medium used in the various embodiments provided herein may include non-volatile and/or volatile memory. The nonvolatile memory can include Read Only Memory (ROM), programmable ROM (PROM), electrically Programmable ROM (EPROM), electrically Erasable Programmable ROM (EEPROM), or flash memory. Volatile memory can include Random Access Memory (RAM) or external cache memory. By way of illustration and not limitation, RAM is available in a variety of forms such as Static RAM (SRAM), dynamic RAM (DRAM), synchronous DRAM (SDRAM), double Data Rate SDRAM (DDRSDRAM), enhanced SDRAM (ESDRAM), synchronous Link DRAM (SLDRAM), memory bus direct RAM (RDRAM), direct memory bus dynamic RAM (DRDRAM), and memory bus dynamic RAM (RDRAM), among others.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Although terms such as leveler, accelerator, suppressor, bath sample, plating bath, and the like are more used herein, the possibility of using other terms is not precluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention; the terms first, second, and the like in the description and in the claims of embodiments of the invention and in the above-described figures, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A method for determining the concentration of an additive in an acidic copper plating solution based on an ultra-microelectrode, wherein the additive mainly comprises an inhibitor, an accelerator and a leveling agent, and the method is characterized by comprising the following steps:
measuring the concentration of the inhibitor, namely diluting a plating solution sample to reduce the influence of an accelerator and a leveling agent in the plating solution sample, and obtaining the concentration of the inhibitor according to the corresponding relation between the dissolved electric quantity of a deposited copper anode and the concentration of the inhibitor;
measuring the concentration of the accelerator, namely adjusting the concentration of the inhibitor and the leveling agent in the plating solution sample to be saturated adsorption concentration, and obtaining the concentration of the accelerator according to the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the accelerator;
and measuring the concentration of the leveling agent, namely preparing electroplating solutions with different concentrations of the leveling agent through known inhibitor concentration and accelerator concentration, and obtaining the concentration of the leveling agent through the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the leveling agent.
2. The method of claim 1, wherein the determination of the inhibitor concentration comprises the steps of:
(1) Preparing electroplating stock solution, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test to measure the stripping electric quantity Q of the deposited copper anode VMS ；
(2) Adding an inhibitor into the electroplating stock solution to form a standard solution A with known inhibitor concentration;
(3) Mixing the standard solution A with the electroplating stock solution according to a certain volume ratio to obtain standard solution B with different known inhibitor concentrations, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test to measure the stripping electric quantity ratio Q/Q of the deposited copper anode VMS Wherein Q and Q VMS Respectively dissolving out electric quantity of the deposited copper anode containing the inhibitor and the deposited copper anode without the inhibitor;
(4) According to the ratio Q/Q of the dissolved electric quantity of the anode of the deposited copper VMS Drawing a standard concentration curve of the inhibitor according to the corresponding relation between the inhibitor concentration and the inhibitor concentration;
(5) Mixing a plating solution sample with an electroplating stock solution according to a certain volume ratio, and measuring the ratio Q of the dissolved electric quantity of a deposited copper anode of the diluted plating solution sample Sample of /Q VMS Will Q Sample of /Q VMS Comparing with the inhibitor concentration standard curve, wherein the corresponding abscissa value is the inhibitor concentration value in the diluted plating solution sample; and calculating the concentration of the inhibitor in the plating solution sample according to the dilution ratio of the plating solution sample.
3. The method according to claim 2, characterized in that: the volume ratio of the plating solution sample to the plating stock solution is (1:50) - (1:1000).
4. The method according to claim 1, characterized in that: the determination of the accelerator concentration comprises the following steps:
(1) Adding an inhibitor and a leveling agent with saturated adsorption concentration into electroplating stock solution to obtain a mixed solution A, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test to measure the stripping electric quantity Q of a deposited copper anode 0 ；
(2) Plating solution sample and mixed solutionA is mixed according to a certain volume proportion to obtain a mixed solution B, a three-electrode system using an ultramicro electrode as a working electrode is adopted to carry out CVS test, and the dissolved electric quantity ratio Q of a deposited copper anode is measured 1 /Q 0 Wherein Q is 1 And Q 0 The dissolved electric quantity of the deposited copper anode containing the accelerator and the deposited copper anode without the accelerator respectively;
(3) Taking i parts of mixed solution B, respectively adding known accelerators with different volumes into the mixed solution B to form a standard solution i, and adopting a three-electrode system with an ultramicro electrode as a working electrode to carry out a stripping voltammetry test to obtain a stripping electric quantity ratio Q of a deposited copper anode 2 /Q 0 ，Q 3 /Q 0 ,......Q i /Q 0 ；
(4) According to the steps (2) and (3), the ratio of the dissolved electric quantity is taken as an ordinate and the concentration of the accelerator is taken as an abscissa, a fitting straight line is formed by the measured ratio of the dissolved electric quantity and the concentration of the accelerator, and the fitting straight line and the straight line y=q are obtained through drawing 0 And (3) obtaining the accelerator concentration of the plating solution sample according to the dilution ratio of the step (2) by the abscissa value of the intersection point.
5. The method according to claim 4, wherein: the volume ratio of the plating solution sample to the mixed solution A is (1:1) - (1:50).
6. The method of claim 1, wherein the determination of leveler concentration comprises the steps of:
(1) Adding inhibitor and accelerator into electroplating stock solution to the same concentration as the inhibitor and accelerator in the plating solution sample to form standard solution C, and measuring the stripping electric quantity Q of the deposited copper anode by using a three-electrode system with an ultramicro electrode as a working electrode to carry out stripping voltammetry test 0 ’；
(2) Adding a leveling agent into the standard solution C to form a standard solution D with known leveling agent concentration;
(3) Mixing the standard solution C and the standard solution D according to a certain volume ratio to obtain solutions with different known leveling agent concentrations, whereinThree-electrode system with ultramicro electrode as working electrode is tested by stripping voltammetry, and the stripping electric quantity ratio Q'/Q of different deposited copper anodes is drawn 0 'wherein Q' and Q 0 ' the dissolved power of the deposited copper anode with and without the leveling agent, respectively;
(4) According to the ratio Q'/Q of the dissolved electric quantity of the anode of the deposited copper 0 ' corresponding relation with leveling agent concentration, drawing a leveling agent standard concentration curve;
(5) The three-electrode system with the ultramicro electrode as the working electrode is adopted to test the plating solution sample by a stripping voltammetry method, and the stripping electric quantity ratio Q of the deposited copper anode of the plating solution sample is measured Sample of ’/Q 0 ' will Q Sample of ’/Q 0 And comparing the' with a standard concentration curve of the leveling agent, wherein the corresponding abscissa value is the concentration of the leveling agent in the sample liquid to be measured.
7. The method according to claim 6, wherein: the volume ratio of the standard solution A to the standard solution B is (1:1) - (1:100).
8. The utility model provides a detection device based on the additive concentration in acid copper plating bath of microelectrode survey, the additive mainly comprises inhibitor, accelerator and leveling agent, characterized by includes:
the inhibitor concentration measuring module is used for diluting the plating solution sample to reduce the influence of an accelerator and a leveling agent in the plating solution sample, and obtaining the concentration of the inhibitor according to the corresponding relation between the dissolved electric quantity of the deposited copper anode and the concentration of the inhibitor;
the accelerator concentration measuring module is used for adjusting the concentration of the inhibitor and the leveling agent in the plating solution sample to the saturated adsorption concentration, and obtaining the concentration of the accelerator according to the corresponding relation between the dissolved electric quantity of the deposited copper anode and the accelerator concentration;
and the leveling agent concentration measuring module is used for preparing electroplating solutions with different leveling agent concentrations through known inhibitor concentrations and accelerator concentrations, and obtaining the concentration of the leveling agent through the corresponding relation between the dissolved electric quantity of the deposited copper anode and the leveling agent concentration.
9. A computer device comprising a memory, a processor, and a computer program stored in the memory and executable on the processor, characterized by: the processor, when executing the computer program, implements the method for determining the concentration of an additive in an acidic copper plating solution based on an ultramicroelectrode as set forth in any one of claims 1 to 7.
10. A computer-readable storage medium storing a computer program, characterized in that: the computer program, when executed by a processor, implements the method for determining the concentration of an additive in an acidic copper plating solution based on an ultramicroelectrode as set forth in any one of claims 1 to 7.
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