CN116297782A - Method, device, equipment and medium for measuring concentration of additive in acidic copper plating solution based on ultramicro electrode - Google Patents

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

A method and device for determining the concentration of additives in acidic copper plating solution based on ultramicroelectrode settings, equipment and media

technical field

The invention relates to the technical field of electrochemical analysis, in particular to a method, device, equipment and medium for measuring the concentration of additives in an acidic copper plating solution based on an ultramicro electrode.

Background technique

The update and iteration of electronic products is inseparable from the support and development of electronic circuit manufacturing technology. Electronic copper plating is one of the core technologies in the field of electronic circuit manufacturing such as printed circuit boards (Printed Circuit Board, PCB), through silicon vias (Through Silicon Via, TSV) and Damascus chips.

Electronic copper plating mainly uses acidic copper sulfate plating solution. In addition to copper sulfate, sulfuric acid and Cl ^- , the acid copper plating solution also contains three types of functional organic additives: inhibitors, accelerators and leveling agents. Inhibitors are usually organic polymer compounds such as polyethylene glycol (PEG), polypropylene glycol (PPG) and ethylene oxide propylene oxide block copolymer (EOPO), etc., by forming inhibitor- The Cl- barrier layer blocks Cu ²⁺ ions from entering the Cu surface and reduces the deposition rate of copper ions. Accelerators such as sodium polydithiodipropanesulfonate (SPS) and 3-mercapto-1-propanesulfonic acid (MPS) are adsorbed on the surface of the cathode through sulfhydryl groups, and the sulfonic acid groups on the other side attract and capture copper ions by electrostatic interaction. to the surface of the cathode to increase the deposition rate of copper ions. Leveling agents are usually nitrogen-containing heterocyclic compounds or quaternary ammonium salts. Common leveling agents are Jianna Green (JGB), Gentian Violet, Diazine Black (DB) and 2-Mercaptopyridine (2-MP), etc. . Leveler molecules usually have one or more positive charges, which are easier to adsorb in high current density areas, inhibit the reduction of copper ions in high current density areas, and achieve the effect of leveling the side walls of micro-vias or blind hole protrusions. In the actual electroplating process, the concentration of additives in the plating solution changes due to factors such as plating parts being carried out and decomposition, which leads to changes in the performance of the plating solution and affects product yield. Therefore, it is very necessary to detect the concentration of organic additives in the acidic copper plating solution.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the above-mentioned prior art, and to provide a method, device, equipment and medium for measuring the concentration of additives in an acidic copper plating solution based on an ultramicroelectrode.

In order to solve the above technical problems, one of the technical solutions provided by the present invention is as follows:

A method for measuring the concentration of additives in an acidic copper plating solution based on an ultramicroelectrode, wherein the additives are mainly composed of inhibitors, accelerators and leveling agents, including:

The determination of inhibitor concentration is to reduce the influence of accelerator and leveling agent in the plating solution sample by diluting the plating solution sample, and then obtain the inhibitor concentration from the corresponding relationship between the electrolytic quantity of the deposited copper anode and the concentration of the inhibitor. concentration;

The determination of the concentration of the accelerator is to obtain the concentration of the accelerator by adjusting the concentration of the inhibitor and leveler in the plating solution sample to the saturated adsorption concentration, and then from the corresponding relationship between the electrolytic quantity of the deposited copper anode and the concentration of the accelerator;

The determination of the concentration of the leveling agent is based on the known concentration of the inhibitor and the concentration of the accelerator, and the electroplating solution with different concentrations of the leveling agent is configured, and then the corresponding relationship between the amount of stripping of the deposited copper anode and the concentration of the leveling agent is obtained to obtain the concentration of the leveling agent. concentration.

In a more preferred embodiment, the determination of the concentration of the inhibitor comprises the following steps:

(1) prepare electroplating stoste, adopt the three-electrode system that is working electrode with ultramicroelectrode to carry out stripping voltammetry test, record deposition copper anode stripping electric quantity Q _VMS ;

(2) Inhibitors are added to the electroplating stock solution to form a standard solution A of known inhibitor concentrations;

(3) The standard solution A is mixed with the electroplating stock solution by a certain volume ratio to obtain the standard solution B with different known inhibitor concentrations, and the stripping voltammetry test is carried out by using a three-electrode system with an ultramicro electrode as the working electrode, and the obtained Deposited copper anode stripping power ratio Q/Q _VMS , where Q and Q _VMS are the stripping power of deposited copper anode with inhibitor and without inhibitor, respectively;

(4) According to the corresponding relationship between the ratio Q/Q _VMS and the inhibitor concentration of the stripping electric quantity of the deposited copper anode, draw the inhibitor standard concentration curve;

(5) Mix the plating solution sample with the electroplating stock solution in a certain volume ratio, measure the ratio Q _sample /Q _VMS of the deposited copper anode stripping electricity of the diluted plating solution sample, and compare the Q _sample /Q _VMS with the inhibitor concentration standard curve , and 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, the inhibitor concentration in the plating solution sample is calculated.

In a more preferred embodiment, the mixing volume ratio of the plating solution sample to the electroplating stock solution is (1:50)˜(1:1000).

In a more preferred embodiment, the mensuration of described accelerator concentration comprises the following steps:

(1) In the electroplating stock solution, an inhibitor and a leveling agent with a saturated adsorption concentration are added to obtain a mixed solution A, and a three-electrode system with an ultra-micro electrode as a working electrode is used for stripping voltammetry testing, and the stripping amount of the deposited copper anode is measured Q ₀ ;

(2) The plating solution sample is mixed with the mixed solution A in a certain volume ratio to obtain the mixed solution B, and the CVS test is carried out by using a three-electrode system with an ultra-micro electrode as the working electrode, and the ratio of the electrolytic quantity Q ₁ / Q ₀ , wherein, Q ₁ and Q ₀ are respectively the amount of electrolytic stripping of deposited copper anodes containing accelerator and without accelerator;

(3) Get i part of mixed solution B, and add different volumes of known accelerators to it respectively to form a standard solution i, and adopt a three-electrode system with an ultramicro electrode as a working electrode to carry out stripping voltammetry test, measure Deposited copper anode stripping electric quantity ratio Q ₂ /Q ₀ , Q ₃ /Q ₀ ,...Q _i /Q ₀ ;

(4) According to steps (2) and (3), take the stripping power ratio as the ordinate and the accelerator concentration as the abscissa, and make a fitting line between the measured stripping power ratio and the accelerator concentration, and obtain the fitting by plotting The abscissa value of straight line and straight line y=Q ₀ intersection point, can obtain the accelerator concentration of plating solution sample according to the dilution ratio of step (2).

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 the leveler concentration comprises the following steps:

(1) Through the known inhibitor concentration and accelerator concentration, add inhibitor and accelerator to the concentration of inhibitor and accelerator in the electroplating stock solution to be equal to the concentration of inhibitor and accelerator in the plating solution sample to form a standard solution C, using an ultra-micro electrode The stripping voltammetry test was carried out for the three-electrode system of the working electrode, and the stripping quantity Q ₀ ' of the deposited copper anode was measured;

(2) Add leveling agent to standard solution C to form standard solution D with known leveling agent concentration;

(3) Standard solution C and standard solution D are mixed according to a certain volume ratio to obtain solutions with different known leveler concentrations, and a three-electrode system with an ultramicro electrode as a working electrode is used for stripping voltammetry testing, and different levels are drawn. Deposited copper anode stripping electricity ratio Q'/Q ₀ ', wherein, Q' and Q ₀ ' are the stripping electricity of deposited copper anode containing leveling agent and not containing leveling agent, respectively;

(4) Draw the standard concentration curve of the leveling agent according to the corresponding relationship between the electrolytic quantity Q'/Q ₀ ' of the deposited copper anode and the concentration of the leveling agent;

(5) Adopting the three-electrode system with the ultramicroelectrode as the working electrode carries out the stripping voltammetry test to the plating solution sample, and measures the deposition copper anode stripping electric quantity ratio Q _sample '/Q ₀ ' of the plating solution sample, and the Q _sample ' /Q ₀ ' is compared with the standard concentration curve of the leveling agent, and the corresponding value on the abscissa is the concentration of the leveling agent in the sample liquid to be tested.

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 solution provided by the present invention is as follows:

A detection device for measuring the concentration of additives in an acidic copper plating solution based on an ultramicro electrode, the additives are mainly composed of inhibitors, accelerators and leveling agents, including:

Inhibitor concentration measurement module is used to dilute the plating solution sample to reduce the influence of accelerators and leveling agents in the plating solution sample, and then obtain the inhibitory The concentration of the agent;

The accelerator concentration measurement module is used to obtain the concentration of the accelerator by adjusting the concentration of the inhibitor and the leveler in the plating solution sample to the saturated adsorption concentration, and then obtaining the concentration of the accelerator from the corresponding relationship between the electrolytic quantity of the deposited copper anode and the concentration of the accelerator;

The leveling agent concentration measurement module is used to configure the electroplating solution with different leveling agent concentrations through the known inhibitor concentration and accelerator concentration, and then obtain the leveling agent from the corresponding relationship between the amount of dissolved copper anode and the concentration of the leveling agent. concentration of the agent.

The third technical scheme provided by the present invention is as follows:

A computer device, comprising a memory, a processor, and a computer program stored in the memory and operable on the processor, when the processor executes the computer program, the ultramicroelectrode-based determination as described above is realized A method for the concentration of additives in acidic copper plating baths.

The fourth technical solution provided by the present invention is as follows:

A computer-readable storage medium, the computer-readable storage medium is stored with a computer program, characterized in that: when the computer program is executed by a processor, it realizes the determination of the additive concentration in the acidic copper plating solution based on the ultra-micro electrode as described above Methods.

In summary, the present application includes at least one of the following beneficial technical effects:

1. It is suitable for real-time monitoring of the concentration of acidic copper plating additives in the electroplating production line.

The technical solution provided by the invention can realize accurate detection of the concentrations of inhibitors, accelerators and leveling agents in the plating solution system, and when measuring the concentration of a single additive, the method can greatly reduce the other two additives in the plating solution It is suitable for the concentration monitoring of electroplating solution additives on the electroplating production line.

2. The method for determining the concentration of additives is simple and fast.

For the detection of inhibitor concentration, only the drawing of a standard curve of inhibitor concentration is involved, and it can be used continuously under the same working conditions, the measurement time is short, and the standard error is within 5%.

For accelerator concentration detection, there is no need to draw a concentration curve, only 6-8 stripping voltammetry scans are required, and the fitting line can be drawn to obtain the accelerator concentration in the plating solution sample, and the error is within 5%;

For the determination of leveler concentration, combined with the detection method of accelerator and inhibitor provided by the present invention, rapid detection can be achieved, and it can also only involve the drawing of a standard curve of leveler concentration, and the error is within 5%.

3. The measuring device is simple and convenient.

The microelectrode used in the invention is used to measure the concentration of three organic additives in the plating solution system. Compared with the traditional rotating disk electrode, the method has the advantages of less liquid consumption and less ohmic pressure drop.

4. Ease of development and application.

The three-electrode system in the method can be applied to a microfluidic device, greatly reducing the amount of plating solution required for analysis of the plating solution, reducing power consumption and low device cost, thereby achieving the goals of energy saving, 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 apparent from the description, or may be learned by practice of the invention. The objectives and other beneficial effects of the present invention can be realized and obtained by the structures particularly pointed out in the specification, claims and accompanying drawings.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative work; the positional relationship described in the drawings in the following description, Unless otherwise specified, the orientation of the components shown in the figure is the reference.

Fig. 1 is a schematic flow sheet of the method for measuring additive concentration in an acidic copper plating solution based on an ultra-microelectrode;

Fig. 2 is the stripping voltammetry curve figure of different inhibitor concentrations;

Fig. 3 is a curve diagram corresponding to the ratio of the stripping electric quantity of the deposited copper anode and the inhibitor concentration;

Fig. 4 is the stripping voltammetry curve figure of plating solution sample and the plating solution sample after dilution;

Fig. 5 is with the deposition copper anode stripping electric quantity ratio of diluted plating solution sample, corresponds to the graph corresponding to the corresponding relation curve of deposition copper anode stripping electric quantity ratio and inhibitor concentration;

Fig. 6 is the stripping voltammetry curve figure that adds different concentration accelerators to draw after the electroplating stoste solution and the plating solution sample that contain inhibitor and accelerator under the saturated adsorption concentration are mixed in a certain proportion;

Fig. 7 is the fitting curve figure that the accelerator concentration in the plating solution sample is calculated, and the absolute value of its abscissa is the accelerator concentration in the plating solution sample;

Fig. 8 is to add the standard curve figure of the leveler of different concentrations in the leveler blank solution (LFE) containing the same inhibitor and accelerator concentration as the plating bath sample;

Fig. 9 is the graph of the relationship between the stripping electricity ratio and the leveler concentration of the leveler with different concentrations added to the leveler blank solution (LFE) containing the same inhibitor and accelerator concentration as the plating bath sample;

Fig. 10 is the stripping voltammetry curve figure of plating solution sample one and plating solution sample two;

Fig. 11 is a graph corresponding to the leveling agent standard concentration curve of the stripping electric quantity of the plating solution sample;

Fig. 12 is the structural representation of the detection device based on ultramicroelectrodes of the present invention to measure the concentration of additives in the acidic copper plating solution;

Fig. 13 is a schematic structural view of a detection device for determining the concentration of additives in an acidic copper plating solution based on an ultramicro electrode according to another embodiment of the present invention;

Fig. 14 is a schematic structural diagram of a computer device of the present invention.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of the embodiments of the present invention, rather than all embodiments; the technical features designed in the different embodiments of the present invention described below can be combined as long as they do not constitute conflicts; based on the embodiments of the present invention, the present invention All other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

In the description of the present invention, it should be noted that all the terms (including technical terms and scientific terms) used in the present invention have the same meanings as commonly understood by those of ordinary skill in the art to which the present invention belongs, and cannot be construed Limitations of the Invention; It should be further understood that the terms used in the present invention should be understood to have a meaning consistent with the meaning of these terms in the context of this specification and in the relevant field, and should not be interpreted in an idealized or overly formal sense , unless explicitly so defined in the present invention.

The invention provides a three-electrode system based on ultra-micro electrodes, based on the corresponding relationship between the amount of dissolved copper anode and the concentration of three additives in the plating solution, and the precise regulation of the influencing factors, to realize the inhibitor and accelerator in the acidic copper plating solution And leveling agent concentration determination method. The ultra-microelectrode has a very thin diffusion layer thickness, which can quickly obtain the kinetic parameters of the electrochemical intrinsic reaction. Using a three-electrode system with an ultra-micro electrode as the working electrode can electrochemically analyze the solution quickly and at low cost; combined with cyclic voltammetry for electrochemical analysis, according to the corresponding relationship between the amount of dissolution of the deposited copper anode and the concentration of the additive, it can be obtained. Determination of the concentrations of inhibitors, accelerators and leveling agents in the plating solution samples, and the influence of other additives can be ignored to a certain extent. In removing the influence of other additives, a special combination of saturated adsorption concentration and dilution is used to Eliminate the influence of other additives to obtain more accurate concentration determination values.

An embodiment of the present invention provides a method for determining the concentration of additives in an acidic copper plating solution based on an ultramicroelectrode. The additives are mainly composed of inhibitors, accelerators and leveling agents, including:

Step 1, the mensuration of inhibitor concentration, by diluting plating solution sample, to reduce the influence of accelerator and leveling agent in plating solution sample, then by the correspondence relation of deposition copper anode stripping electricity and inhibitor concentration, draw the concentration of the inhibitor;

Step 2, the mensuration of accelerator concentration, by adjusting the concentration of inhibitor and leveling agent in the plating solution sample to the saturated adsorption concentration, and then by the corresponding relationship between the stripping amount of deposited copper anode and the concentration of accelerator, the concentration of accelerator is obtained ;

Step 3, the determination of the concentration of the leveling agent, through the known concentration of the inhibitor and the concentration of the accelerator, the electroplating solution with different concentrations of the leveling agent is configured, and then the corresponding relationship between the amount of dissolution of the deposited copper anode and the concentration of the leveling agent is obtained. leveling agent concentration.

It should be noted that in the description of this embodiment, the continuous labeling of the method steps is for the convenience of review and understanding, combined with the overall technical solution of this embodiment and the logical relationship between each step, to adjust the implementation of some steps The sequence will not affect the technical effect achieved by the technical solution of this embodiment. The content of each step is discussed in detail below:

In one embodiment, the determination of the concentration of the inhibitor comprises the following steps:

(1) prepare electroplating stock solution (VMS), adopt the three-electrode system that is working electrode with ultramicroelectrode to carry out stripping voltammetry test, record deposition copper anode stripping electric quantity Q _VMS ;

(2) Inhibitors are added to the electroplating stock solution to form a standard solution A of known inhibitor concentrations;

(3) Mix the standard solution A with the electroplating stock solution by a certain volume ratio to obtain the standard solution B with different known inhibitor concentrations, and use the three-electrode system with the ultramicro electrode as the working electrode to carry out the stripping voltammetry (CVS) test , the ratio Q/Q _VMS of the stripped copper anode was measured, wherein Q and Q _VMS were the stripped copper anode stripped with inhibitor and without inhibitor respectively;

(4) According to the corresponding relationship between the ratio Q/Q _VMS and the inhibitor concentration of the stripping electric quantity of the deposited copper anode, draw the inhibitor standard concentration curve;

(5) Mix the plating solution sample with the electroplating stock solution in a certain volume ratio, measure the ratio Q _sample /Q _VMS of the deposited copper anode stripping electricity of the diluted plating solution sample, and compare the Q _sample /Q _VMS with the inhibitor concentration standard curve , the corresponding abscissa value is the inhibitor concentration value in the plating solution sample after dilution; calculate the inhibitor concentration in the plating solution sample according to the dilution ratio of the plating solution sample;

Preferably, the mixing volume ratio of the plating solution sample to the electroplating stock solution is (1:50)˜(1:1000).

In one embodiment, the determination of the accelerator concentration comprises the following steps:

(1) An inhibitor with a saturated adsorption concentration of 100-1000ppm and a leveler with a saturated adsorption concentration of 10-100ppm can be added to the electroplating stock solution to obtain a mixed solution A, using a three-electrode system with an ultra-micro electrode as the working electrode Carry out the stripping voltammetry test, and measure the stripping quantity Q ₀ of the deposited copper anode;

(2) The plating solution sample is mixed with the mixed solution A in a certain volume ratio to obtain the mixed solution B, and the CVS test is carried out by using a three-electrode system with an ultra-micro electrode as the working electrode, and the ratio of the electrolytic quantity Q ₁ / Q ₀ , wherein, Q ₁ and Q ₀ are respectively the amount of electrolytic stripping of deposited copper anodes containing accelerator and without accelerator;

Preferably, the volume ratio of the plating solution sample to the mixed solution A is (1:1)˜(1:50).

(3) Get i part of mixed solution B, and add different volumes of known accelerators to it respectively to form a standard solution i, and adopt a three-electrode system with an ultramicro electrode as a working electrode to carry out stripping voltammetry test, measure Deposited copper anode stripping electric quantity ratio Q ₂ /Q ₀ , Q ₃ /Q ₀ ,...Q _i /Q ₀ ;

(4) According to steps (2) and (3), take the stripping power ratio as the ordinate and the accelerator concentration as the abscissa, and make a fitting line between the measured stripping power ratio and the accelerator concentration, and obtain the fitting by plotting The abscissa value of straight line and straight line y=Q ₀ intersection point, can obtain the accelerator concentration of plating solution sample according to the dilution ratio of step (2).

In one embodiment, the determination of the leveler concentration comprises the following steps:

(1) Through the known inhibitor concentration and accelerator concentration, add inhibitor and accelerator to the concentration of inhibitor and accelerator in the electroplating stock solution to be equal to the concentration of inhibitor and accelerator in the plating solution sample to form a standard solution C, using an ultra-micro electrode The stripping voltammetry test was carried out for the three-electrode system of the working electrode, and the stripping quantity Q ₀ ' of the deposited copper anode was measured;

(2) Add leveling agent to standard solution C to form standard solution D with known leveling agent concentration;

(3) Standard solution C and standard solution D are mixed according to a certain volume ratio to obtain solutions with different known leveler concentrations, and a three-electrode system with an ultramicro electrode as a working electrode is used for stripping voltammetry testing, and different levels are drawn. Deposited copper anode stripping electricity ratio Q'/Q ₀ ', wherein, Q' and Q ₀ ' are the stripping electricity of deposited copper anode containing leveling agent and not containing leveling agent, respectively;

Preferably, the volume ratio of the standard solution C to the standard solution D is (1:1) to (1:100);

(4) Draw the standard concentration curve of the leveling agent according to the corresponding relationship between the electrolytic quantity Q'/Q ₀ ' of the deposited copper anode and the concentration of the leveling agent;

(5) Adopting the three-electrode system with the ultramicroelectrode as the working electrode carries out the stripping voltammetry test to the plating solution sample, and measures the deposition copper anode stripping electric quantity ratio Q _sample '/Q ₀ ' of the plating solution sample, and the Q _sample ' /Q ₀ ' is compared with the standard concentration curve of the leveling agent, and the corresponding value on the abscissa is the concentration of the leveling agent in the sample liquid to be tested.

In a preferred embodiment, the ultramicro electrodes include but are not limited to platinum electrodes and silver electrodes, and the diameter of the ultramicro electrodes ranges from more than 1 μm to less than 50 μm.

In a preferred embodiment, the range of potential scanning in the electrochemical experiment is above -0.8V and below 1.5V.

Wherein, inhibitor includes but not limited to polyethylene glycol, ethylene oxide propylene oxide block copolymer and polypropylene glycol etc.; -1-propanesulfonic acid, etc.; leveling agents include but are not limited to nitrogen-containing heterocyclic compounds or quaternary ammonium salts such as Jianna green, gentian violet, diazine black, and 2-mercaptopyridine.

The technical solution of the present invention is further illustrated and described through specific examples below, but the protection scope of the present invention is not limited thereto.

Example 1

Please refer to Fig. 1-5, present embodiment carries out the concentration determination of inhibitor in the acidic copper plating solution;

Experimental equipment and experimental conditions:

Experimental equipment: electrochemical workstation CHI760E, magnetic stirrer, ultrasonic cleaner.

Working electrode: 25μm platinum ultramicro electrode; reference electrode: mercurous sulfate electrode; auxiliary electrode:

Platinum electrodes.

Experimental conditions: room temperature

Analysis steps:

Step 1. Prepare an electroplating stock solution, which generally contains the following components: 50-80g/L CuSO ₄ ·5H ₂ O, 140-200g/L H ₂ SO ₄ , 40-80mg/L Cl ^- ;

In this example 1, the components of the prepared electroplating stock solution are as follows: 75g/L CuSO ₄ ·5H ₂ O, 180g/L H ₂ SO ₄ , 60mg/L NaCl;

Step 2. Prepare a plating solution sample, which generally contains the following components: 50-80g/L CuSO ₄ ·5H ₂ O, 140-200g/L H ₂ SO ₄ , 40-80mg/L Cl ⁻ , PEG of 200-800mg/L (molecular weight is 8000), SPS of 1.0mg/L, JGB of 1-10mg/L;

In this embodiment 1, the concentration of the inhibitor is measured on the prepared plating solution sample containing the following components: CuSO ₄ 5H ₂ O of 75g/L, H ₂ SO ₄ of 180g/L, NaCl of 60mg/L, 300mg/L inhibitor PEG (molecular weight is 8000), 1mg/L accelerator SPS, 3mg/L leveler JGB;

Step 3, drawing of inhibitor standard concentration curve: Add inhibitors of different concentrations as shown in Figure 2 in the electroplating stock solution, such as 5ppm, 10ppm, 15ppm, 17.5ppm, 20ppm, 22,5ppm, 30ppm, and dissolve Voltammetry test, the concentration of the inhibitor is used as the abscissa, and the ratio of the stripping electricity of the deposited copper anode is taken as the ordinate, and the corresponding relationship curve between the stripping electricity ratio and the concentration of the inhibitor is drawn;

Step 4, dilute the plating solution sample by 50 times, and use the three-electrode system with the ultra-micro electrode as the working electrode to carry out the CVS test to obtain the stripping power ratio;

Step 5, the stripping electricity ratio of the diluted plating solution sample is corresponding to the corresponding relationship curve of the deposition copper anode stripping electricity ratio and the concentration of the inhibitor, and the calculation can obtain the inhibitor concentration (6.05mg/L) in the plating solution sample), the The experimental error of the example is 0.8%.

Further, please refer to Fig. 1 and Fig. 6-7, carry out the determination of accelerator concentration in plating solution;

Experimental equipment and experimental conditions:

Experimental equipment: electrochemical workstation CHI760E, magnetic stirrer, ultrasonic cleaner.

Working electrode: 25 μm platinum ultramicro electrode; reference electrode: mercurous sulfate electrode; auxiliary electrode: platinum sheet electrode.

Experimental conditions: room temperature

Analysis steps:

Step 1. Prepare an electroplating stock solution, which generally contains the following components: 50-80g/L CuSO ₄ ·5H ₂ O, 140-200g/L H ₂ SO ₄ , 40-80mg/L Cl ^- ;

In this example 1, the components of the prepared electroplating stock solution are as follows: 75g/L CuSO ₄ ·5H ₂ O, 180g/L H ₂ SO ₄ , 60mg/L NaCl;

Step 2. Prepare a plating solution sample, which generally contains the following components: 50-80g/L CuSO ₄ ·5H ₂ O, 140-200g/L H ₂ SO ₄ , 40-80mg/L Cl ⁻ , PEG of 200-800mg/L (molecular weight is 8000), SPS of 1.0mg/L, JGB of 1-10mg/L;

In this embodiment 1, the concentration determination of the accelerator is carried out on the plating solution sample containing the following components: CuSO ₄ 5H ₂ O of 75g/L, H ₂ SO ₄ of 180g/L, NaCl of 60mg/L, 300mg/L inhibitor PEG (molecular weight is 8000), 1mg/L accelerator SPS, 3mg/L leveler JGB;

Step 3. Add 300 mg/LPEG and excess JGB to the electroplating stock solution, and use a three-electrode system with an ultramicro electrode as the working electrode to perform stripping voltammetry test to obtain the stripping power ratio of the deposited copper anode;

Step 4. Mix the plating solution sample (1.00ppm) with the liquid in the analysis step 3 at a ratio of 1:4, and use a three-electrode system with an ultra-micro electrode as the working electrode to perform stripping voltammetry testing to obtain its deposited copper anode stripping Power ratio;

Step 5, in the liquid in analysis step 4, add the accelerator standard solution (concentration known) of different volumes as shown in Figure 6 successively, as 0.1ppm, 0.2ppm, 0.6ppm, adopt the ultramicroelectrode as working electrode The stripping voltammetry test was carried out on the three-electrode system to obtain the stripping electric quantity ratio of the deposited copper anode;

Step 6, fitting a straight line, the absolute value of the abscissa multiplied by the dilution factor is the accelerator concentration (0.955ppm) in the plating solution sample, and the experimental error of this example is 4.5%.

Further, please refer to Figure 1 and Figure 8-11 to measure the concentration of the leveling agent in the plating solution;

Experimental equipment and experimental conditions:

Experimental equipment: electrochemical workstation CHI760E, magnetic stirrer, ultrasonic cleaner.

Working electrode: 25 μm platinum ultramicro electrode; reference electrode: mercurous sulfate electrode; auxiliary electrode: platinum sheet electrode.

Experimental conditions: room temperature

Analysis steps:

Step 1. Prepare an electroplating stock solution, which generally contains the following components: 50-80g/L CuSO ₄ ·5H ₂ O, 140-200g/L H ₂ SO ₄ , 40-80mg/L Cl ^- ;

In this example 1, the components of the prepared electroplating stock solution are as follows: 75g/L CuSO ₄ ·5H ₂ O, 180g/L H ₂ SO ₄ , 60mg/L NaCl;

Step 2. Prepare a plating solution sample, which generally contains the following components: 50-80g/L CuSO ₄ ·5H ₂ O, 140-200g/L H ₂ SO ₄ , 40-80mg/L Cl ⁻ , the PEG of 300mg/L (molecular weight is 8000), the SPS of 1-10mg/L, the JGB of 2.50mg/L;

In this embodiment 1, the plating solution sample one and the plating solution sample two containing the following components are configured to measure the leveler concentration, wherein the inhibitor concentration and the accelerator concentration in the plating solution sample one and the plating solution sample two are Measured using the aforementioned method and known:

The composition of plating solution sample 1: CuSO ₄ 5H ₂ O of 75g/L, H ₂ SO ₄ of 180g/L, NaCl of 60mg/L, inhibitor PEG (molecular weight is 8000) of 300mg/L, 1mg/L of Accelerator SPS, 2.5mg/L leveler JGB;

The composition of plating solution sample two: CuSO ₄ 5H ₂ O of 75g/L, H ₂ SO ₄ of 180g/L, NaCl of 60mg/L, inhibitor PEG (molecular weight is 8000) of 300mg/L, 1mg/L of Accelerator SPS, 3.5mg/L leveler JGB;

Step 3, drawing of standard concentration curve of leveling agent: Add inhibitor PEG (300mg/L) and accelerator SPS (1mg/L) of the same concentration as the plating solution sample to the electroplating stock solution, and add them sequentially as shown in Figure 8 Different volumes of 1g/LJGB standard solutions, such as 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, were tested by stripping voltammetry using a three-electrode system with an ultra-micro electrode as the working electrode, and the relationship between the ratio of the stripping electricity and the concentration of the leveling agent was drawn. Corresponding relationship curve;

Step 4, adopting the three-electrode system with the ultramicro electrode as the working electrode carries out the stripping voltammetry test to the plating solution sample (actual concentration is 2.50ppm and 3.50ppm), obtains the stripping electric quantity ratio of its deposited copper anode;

Step 5, the stripping electricity ratio of the diluted plating solution sample is corresponding to the corresponding relationship curve of the stripping electricity ratio and the leveler concentration, and the JGB concentration (2.54ppm and 3.46ppm) in the plating solution sample can be calculated, the example's The average experimental error was 1.3%.

Above embodiment provides the measuring method of inhibitor, accelerator, leveling agent respectively, and based on above-mentioned method formation with inhibitor or accelerating agent's first mensuration, and then completes the leveling agent concentration determination of plating solution sample, thereby obtains a It is faster and more accurate to complete the determination methods of the above three additives.

Example 2

Please refer to Fig. 12 and Fig. 13, provide a kind of detection device based on ultramicroelectrode determination additive concentration in the acidic copper plating solution, described additive is mainly made up of inhibitor, accelerator and leveling agent, comprises:

Inhibitor concentration measurement module 10 is used to dilute the plating solution sample to reduce the influence of accelerators and leveling agents in the plating solution sample, and then obtain the corresponding relationship between the amount of dissolved copper anode and the concentration of the inhibitor by diluting the plating solution sample. the concentration of the inhibitor;

The accelerator concentration measurement module 20 is used to obtain the concentration of the accelerator by adjusting the concentration of the inhibitor and the leveler in the plating solution sample to the saturated adsorption concentration, and then from the corresponding relationship between the amount of stripping of the deposited copper anode and the concentration of the accelerator ;

The leveling agent concentration measurement module 30 is used to configure electroplating solutions with different leveling agent concentrations through the known inhibitor concentration and accelerator concentration, and then obtain the leveling agent concentration from the corresponding relationship between the amount of stripped copper anode and the leveling agent concentration. leveling agent concentration.

Example 3

Please refer to FIG. 14 , the present invention provides a computer device, including a memory, a processor, and a computer program stored in the memory and operable on the processor. When the processor executes the computer program, the above-mentioned The method for determining the concentration of additives in the acidic copper plating solution based on the ultramicroelectrode in the embodiment, such as the steps shown in FIG. 1 , will not be repeated here to avoid repetition. Alternatively, when the processor executes the computer program, the functions of each module/unit of the detection device for determining the concentration of additives in the acidic copper plating solution based on the ultramicroelectrodes in the above embodiments are realized, such as the functions of modules 10 to 30 shown in FIG. 12 . To avoid repetition, details are not repeated here.

Example 4

In one embodiment, the present invention provides a computer-readable storage medium, the computer-readable storage medium stores a computer program, and when the computer program is executed by a processor, the method of measuring acidity based on an ultramicroelectrode in the above-mentioned embodiment is realized. The method for the concentration of additives in the copper plating solution, such as the steps shown in Figure 1, will not be repeated here in order to avoid repetition. Alternatively, when the processor executes the computer program, the functions of each module/unit of the detection device for determining the concentration of additives in the acidic copper plating solution based on the ultramicroelectrodes in the above embodiments are realized, such as the functions of modules 10 to 30 shown in FIG. 12 . To avoid repetition, details are not repeated here.

Those of ordinary skill in the art can understand that all or part of the processes in the methods of the above-mentioned embodiments can be completed by instructing related hardware through computer programs, and the computer programs can be stored in a non-volatile computer-readable memory In the medium, when the computer program is executed, it may include the processes of the embodiments of the above-mentioned methods. Wherein, any references to memory, storage, database or other media used in the various embodiments provided in the present application may include non-volatile and/or volatile memory. 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 many forms such as Static RAM (SRAM), Dynamic RAM (DRAM), Synchronous DRAM (SDRAM), Double Data Rate SDRAM (DDRSDRAM), Enhanced SDRAM (ESDRAM), Synchronous Chain Synchlink DRAM (SLDRAM), memory bus (Rambus) direct RAM (RDRAM), direct memory bus dynamic RAM (DRDRAM), and memory bus dynamic RAM (RDRAM), etc.

In addition, those skilled in the art should understand that although there are many problems in the prior art, each embodiment or technical solution of the present invention can only be improved in one or several aspects, and it is not necessary to solve the problems in the prior art or at the same time. All technical problems listed in the background technology. It should be understood by those skilled in the art that anything that is not mentioned in a claim should not be taken as a limitation on the claim.

Although terms such as leveling agent, accelerator, inhibitor, plating solution sample, and electroplating stock solution are frequently used in this paper, the possibility of using other terms is not excluded. These terms are only used to describe and explain the essence of the present invention more conveniently; interpreting them as any kind of additional limitation is against the spirit of the present invention; the description and claims of the embodiments of the present invention and the above appended The terms "first", "second", etc. in the drawings, if present, are used to distinguish similar items and are not necessarily used to describe a specific order or sequence.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. scope.

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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