JP6777503B2 - Electroplating solution analyzer, electroplating solution analysis method and electrolytic plating solution analysis program - Google Patents

Description

The present invention relates to an electroplating solution analyzer for analyzing the state of an electroplating solution, an electroplating solution analysis method, and a program for electroplating solution analysis.

For example, the following patent documents include a copper sulfate plating solution containing chloride ions, nonionic polyether-based polymer surfactants, sulfur-containing organic compounds, nitrogen-containing organic compounds, and the like (hereinafter, "electrolytic plating solution"). The invention of an analysis method for analyzing the concentration of a nitrogen-containing organic compound (nitrogen-containing organic compound-based additive) is disclosed. In this analysis method, the integrated area of the negative current portion generated when the concentration of the sulfur-containing organic compound is changed in the electrolytic plating solution to which chloride ions and nonionic polyether polymer surfactants are excessively added, A calibration curve was created and created based on the relationship between the amount of change in the integrated area of the positive current portion or the rate of change in the integrated area of the positive current portion and the concentration of the nitrogen-containing organic compound contained in the electrolytic plating solution. A method of specifying the concentration of the nitrogen-containing organic compound contained in the electrolytic plating solution based on the calibration curve is adopted.

Japanese Unexamined Patent Publication No. 2009-52118 (pages 5-18, Fig. 1-2)

In the analysis method disclosed in the above patent document, the concentration of the nitrogen-containing organic compound is based on a calibration curve prepared based on the relationship between the parameter that changes according to the change in the concentration of the sulfur-containing organic compound and the concentration of the nitrogen-containing organic compound. Is specified. As a result, according to this analysis method, the concentration of the nitrogen-containing organic compound-based additive contained in the copper sulfate plating solution containing a plurality of additives can be specified with good reproducibility and high accuracy. It is possible.

However, in the above analysis method for the purpose of specifying the concentration of the nitrogen-containing organic compound (nitrogen-containing organic compound-based additive), the concentration of the content other than the nitrogen-containing organic compound contained in the electrolytic plating solution to be analyzed. Cannot be specified. Therefore, when it is necessary to specify the concentration of the content other than the nitrogen-containing organic compound, the concentration of the target content is separated from the treatment for specifying the concentration of the nitrogen-containing organic compound based on the calibration curve as described above. It is necessary to execute each of the specific processes of. Therefore, the above-mentioned analysis method has a problem that a very long working time is required to specify the concentration of each of a plurality of types of inclusions contained in the electrolytic plating solution.

The present invention has been made in view of the above problems, and an electrolytic plating solution analyzer, an electrolytic plating solution analysis method, and an electrolytic plating solution analysis method capable of identifying the concentrations of a plurality of types of inclusions contained in the electrolytic plating solution in a short time. The main purpose is to provide a program for electroplating solution analysis.

In order to achieve the above object, the electrolytic plating solution analyzer according to claim 1 performs an analysis process for analyzing the state of the electrolytic plating solution based on the measurement result of the electrochemical measurement process for the electrolytic plating solution to be analyzed. It is provided with a processing unit to be executed and a storage unit for storing concentration specifying data for specifying the concentration of N kinds (N is a natural number of 2 or more) contained in the electrolytic plating solution. As the concentration identification data, the storage unit targets a plurality of types of samples containing the same metal ions as the electrolytic plating solution and having different combinations of concentrations of the respective inclusions at a plurality of types of reduction potentials. The values of a plurality of types of analytical parameters for each reduction potential specified for each sample based on the measurement results of the electrochemical measurement processing executed respectively are the concentration of each content in each sample and the said. Stores the first data recorded in association with the value of the reduction potential and the second data of a predetermined analytical model formula showing the correlation between the concentration of each of the inclusions and the parameters for each analysis. Then, in the analysis process, the processing unit sets the value of each analysis parameter in the first data and the value indicating the concentration of each of the inclusions in the second reduction potential of each sample. From the plurality of first model formulas substituted into the analytical model formulas in the data, the first model formula for specifying the first model formula satisfying the first predetermined criterion for each of the inclusions. And the measurement result of the electrochemical measurement process executed for the electrolytic plating solution at the reduction potential associated with the N first model formulas specified by the first process. At the same time, each of the second model equations in which the values of the plurality of types of analytical parameters specified based on the acquired measurement results are substituted into the analytical model equations corresponding to the N first model equations. Based on the above, a second treatment for specifying the concentration of each of the inclusions in the electrolytic plating solution is performed.

Further, the electrolytic plating solution analyzer according to claim 2 is the electrolytic plating solution analyzer according to claim 1, wherein the storage unit uses the concentration of each of the inclusions and the parameters for analysis as the second data. The plurality of types of the analysis model formulas showing the correlation of the above are stored, and the processing unit stores the plurality of types of the first model formulas corresponding to the plurality of types of analysis model formulas in the first processing. Among them, the first model formula of the type satisfying the second standard specified in advance is specified, and from each of the specified first model formulas, the first standard is used for each of the inclusions. The first model equation that satisfies the condition is specified.

Further, the electrolytic plating solution analyzer according to claim 3 is a measuring unit that executes the electrochemical measurement process for the electrolytic plating solution and each sample in the electrolytic plating solution analyzer according to claim 1 or 2. The processing unit generates the first data based on the measurement result of the electrochemical measurement processing for each reduction potential of each sample by the measuring unit and stores the first data in the storage unit. At the same time, in the second treatment, the values of the plurality of types of analytical parameters are specified based on the measurement results of the electrochemical measurement treatment for the electrolytic plating solution by the measuring unit, and the contents of each of the inclusions are specified. Identify the concentration.

Further, the electrolytic plating solution analysis method according to claim 4 includes measurement results of an electrochemical measurement process for the electrolytic plating solution to be analyzed, and N types (N is 2 or more) contained in the electrolytic plating solution. In the analysis process for analyzing the state of the electrolytic plating solution based on the concentration specifying data for identifying the concentration of the content (natural number) of the above, the same metal ion as the electrolytic plating solution is used as the concentration specifying data. Is specified for each sample based on the measurement results of the electrochemical measurement process executed at a plurality of types of reduction potentials for a plurality of types of samples containing the above substances and having different combinations of concentrations of the respective contents. Each analytical parameter in the first data recorded in association with the concentration of each content in each sample and the value of the reduction potential in which the values of the plurality of types of analytical parameters for each reduction potential are recorded. And a value indicating the concentration of each of the inclusions, for each reduction potential of each of the samples, a predetermined analytical model formula showing the correlation between the concentration of each inclusion and the parameters for analysis. From the plurality of first model formulas substituted into the analytical model formulas in the second data of the above, the first model formula satisfying the first predetermined criterion for each of the inclusions is selected. Of the first process to be identified and the electrochemical measurement process performed on the electrolytic plating solution at the reduction potentials associated with the N first model equations specified by the first process. Each of the measurement results is acquired and the values of the plurality of types of analytical parameters specified based on the acquired measurement results are substituted into the analytical model equations corresponding to the N first model equations. Based on the model formula of 2, the second process of specifying the concentration of each of the contents in the electrolytic plating solution is executed.

Further, the electrolytic plating solution analysis method according to claim 5 corresponds to the plurality of types of analytical model formulas in the second data in the first process in the electrolytic plating solution analysis method according to claim 4. Among the plurality of types of the first model formulas, the first model formulas of the type satisfying the predetermined second criterion are specified, and each of the specified first model formulas is selected. For each inclusion, the first model formula that meets the first criterion is specified.

Further, the electrolytic plating solution analysis program according to claim 6 is a process of executing an analysis process for analyzing the state of the electrolytic plating solution based on the measurement result of the electrochemical measurement process for the electrolytic plating solution to be analyzed. Electrolytic plating including a part and a storage part for storing concentration identification data for specifying the concentration of N kinds (N is a natural number of 2 or more) contained in the electrolytic plating solution. This is an electrolytic plating solution analysis program for causing the processing unit of the liquid analyzer to execute the analysis process, and the storage unit contains the same metal ions as the electrolytic plating solution as the concentration identification data, and each of the above. Each reduction potential specified for each sample based on the measurement result of the electrochemical measurement process executed at a plurality of types of reduction potentials for a plurality of types of samples having different combinations of content concentrations. The first data in which the values of a plurality of types of analytical parameters for each are recorded in association with the concentration of each content in each sample and the value of the reduction potential, the concentration of each content and each analysis. In a state in which the second data of the predetermined analysis model formula showing the correlation of the parameters for analysis is stored, the analysis of the first data in the analysis process is performed on the processing unit. From among a plurality of first model equations in which the values of the parameters and the values indicating the concentrations of the respective inclusions are substituted into the analytical model equations in the second data for each reduction potential of each sample. For each of the inclusions, a first process for specifying the first model formula satisfying a predetermined first criterion, and N pieces of the first model formula specified by the first process. The measurement results of the electrochemical measurement process performed on the electrolytic plating solution at the reduction potential associated with the above are acquired, and the plurality of types of analytical parameters specified based on the acquired measurement results. Based on each second model formula in which the value of is substituted into the analytical model formula corresponding to the N first model formulas, a second model formula for specifying the concentration of each content in the electrolytic plating solution. Process and execute.

Further, the electrolytic plating solution analysis program according to claim 7 is the electrolytic plating solution analysis program according to claim 6, wherein the concentration of each of the inclusions and each analysis are stored in the storage unit as the second data. In a state where a plurality of types of the analysis model formulas indicating the correlation of the parameters for analysis are stored, a plurality of types corresponding to the plurality of types of analysis model formulas are stored in the first processing for the processing unit. From the first model formula of the above, the first model formula of the kind satisfying the second criterion specified in advance is specified, and from each of the specified first model formulas, the respective inclusions. Each time, a process for specifying the first model formula that satisfies the first criterion is executed.

The electrolytic plating solution analyzer according to claim 1 and the electrolytic plating solution analysis method according to claim 4 are based on the measurement results of electrochemical measurement processing performed on a plurality of types of samples at a plurality of types of reduction potentials. For each analysis in the first data recorded in which the values of a plurality of types of analytical parameters for each reduction potential specified for each sample are associated with the concentration of each content in each sample and the value of the reduction potential. The value of the parameter and the value indicating the concentration of each inclusion are the second of the predetermined analytical model formulas showing the correlation between the concentration of each inclusion and each analysis parameter for each reduction potential of each sample. A first process for specifying a first model formula that satisfies a predetermined first criterion for each content from among a plurality of first model formulas substituted for the analysis model formulas in the data. , The measurement result of the electrochemical measurement process performed on the electrolytic plating solution at the reduction potential associated with the specified N first model formulas is acquired, and is specified based on the acquired measurement result. The concentration of N types of inclusions in the electrolytic plating solution is specified based on each second model formula in which the values of a plurality of types of analytical parameters are substituted into the analytical model formulas corresponding to the N first model formulas. The second process to be performed is executed. Further, in the electrolytic plating solution analysis program according to claim 6, the processing unit in the electrolytic plating solution analyzer is made to execute the first process and the second process.

Therefore, according to the electroplating solution analyzer according to claim 1, the electroplating solution analysis method according to claim 4, and the electroplating solution analysis program according to claim 6, N types contained in the electrolytic plating solution. Since the concentration of the inclusions in the above can be specified in one operation, the concentration of each inclusion in the electroplating solution, which often contains multiple types of inclusions, should be specified in a short time. Can be done. In addition, by executing the first treatment once, when the concentration of each content contained in the electrolytic plating solution should be specified, only the second treatment is executed to analyze the analysis result (contents). Since the concentration) can be obtained, the state of the electrolytic plating solution can be sequentially grasped, and the object can be plated under suitable conditions.

In the electrolytic plating solution analyzer according to claim 2 and the electrolytic plating solution analysis method according to claim 5, in the first process, a plurality of types of first types corresponding to a plurality of types of analytical model formulas in the second data. From the model formulas of the above, the first model formula of the type satisfying the second predetermined standard is specified, and from each of the specified first model formulas, the first standard is used for each content. Identify a first model equation that satisfies. Further, in the electrolytic plating solution analysis program according to claim 7, in the first process, the processing unit in the electrolytic plating solution analyzer is made to execute the above processing.

Therefore, according to the electroplating solution analyzer according to claim 2, the electroplating solution analysis method according to claim 5, and the electroplating solution analysis program according to claim 7, the characteristics of the inclusion whose concentration should be specified are determined. By preparing a plurality of types of analytical model formulas according to the situation, the concentrations of various inclusions can be accurately specified.

In the electrolytic plating solution analyzer according to claim 3, the processing unit generates first data based on the measurement result of the electrochemical measurement processing for each reduction potential of each sample by the measuring unit and stores it in the storage unit. In addition to being memorized, in the second process, the values of a plurality of types of analytical parameters are specified based on the measurement results of the electrochemical measurement process for the electrolytic plating solution by the measuring unit to specify the concentration of each content. .. Therefore, according to the electrolytic plating solution analyzer according to claim 3, the concentration of each content contained in the electrolytic plating solution is preferably specified without providing an electrochemical measuring device separately from the electrolytic plating solution analyzer. be able to.

It is a block diagram of the electrolytic plating solution analysis system 1. It is explanatory drawing for demonstrating the sample used in the analysis process. It is explanatory drawing for demonstrating the analytical parameter (current efficiency and plating amount) specified for each reduction potential for each sample.

Hereinafter, an electroplating solution analyzer, an electroplating solution analysis method, and an embodiment of an electroplating solution analysis program will be described with reference to the accompanying drawings.

The electrolytic plating solution analysis system 1 shown in FIG. 1 is an "electroplating solution analyzer" capable of analyzing the state of the electrolytic plating solution (plating bath) Xa stored in the plating solution tank according to the "electroplating solution analysis method". This is an example of the above, and is configured to include an electrochemical measuring device 2 and an analyzer 3.

The electrochemical measuring device 2 includes an electrochemical sensor 2a and a measuring device main body 2b. The electrochemical sensor 2a is a sensor device for executing "electrochemical measurement processing" by tripolar measurement, and includes a casing 10, a reference electrode 11, a working electrode 12, a counter electrode 13, and a signal processing circuit board 14. There is. In this specification, the reference electrode 11, the working electrode 12, and the counter electrode 13 have the same shape and the same size in order to facilitate the understanding of the “electroplating solution analyzer” and the “electroplating solution analysis method”. Although shown in the figure, in reality, various shapes, sizes, and configurations of each electrode 11 to 13 are formed according to the type of the electrolytic plating solution Xa of the measurement target (analysis target by the electrolytic plating solution analysis system 1). Electrodes are adopted.

The casing 10 is a container body made of a chemical resistant resin material or the like, and accommodates the signal processing circuit boards 14 connected to the electrodes 11 to 13 as well as to which the electrodes 11 to 13 are attached. The signal processing circuit board 14 is a circuit board on which a potentiostat, an I / V conversion circuit, and the like are mounted, and is connected to the measuring device main body 2b via a signal cable 2c. The signal processing circuit board 14 can also be a component on the measuring device main body 2b side.

The measuring device main body 2b includes an operation unit 21, a display unit 22, a processing unit 23, and a storage unit 24. The operation unit 21 is provided with an operation switch capable of performing operations such as setting operations such as measurement conditions, instructions for starting / stopping various processes, and instructions for transmitting measurement results to the analyzer 3, and operations corresponding to these operations. The signal is output to the processing unit 23. The display unit 22 displays the measurement result of the electrochemical measurement process calculated by the processing unit 23 under the control of the processing unit 23.

The processing unit 23 comprehensively controls the electrochemical measuring device 2. Specifically, the processing unit 23 constitutes a "measuring unit" in combination with the signal processing circuit board 14 of the electrochemical sensor 2a, and "electrochemical measurement processing (hereinafter, hereinafter)" is performed in response to an operation signal from the operation unit 21. , Simply "measurement processing") "and so on. In this case, the processing unit 23 controls the potential of the working electrode 12 with respect to the reference electrode 11 (hereinafter, also simply referred to as “the electrode potential of the working electrode 12”) while controlling the current flowing between the counter electrode 13 and the working electrode 12. The current value (sensor signal output from the electrochemical sensor 2a) is acquired, the measured value is calculated based on the acquired current value (sensor signal value), and the calculation result (measured value: "electrochemical measurement process". A process of generating the measured value data D1 in which an example of the “measurement result”) is recorded and storing it in the storage unit 24 is executed as the “measurement process”.

Further, the processing unit 23 reads the measured value data D1 from the storage unit 24 in response to the operation signal from the operation unit 21 (or the control signal from the analyzer 3) and outputs the measured value data D1 to the analyzer 3. The storage unit 24 stores the operation program of the processing unit 23, the above-mentioned measured value data D1, and the like.

On the other hand, the analyzer 3 is composed of a personal computer in which the analysis program Dp corresponding to the "electroplating solution analysis program" is installed, as an example, and includes an operation unit 31, a display unit 32, a processing unit 33, and a storage unit. The unit 34 is provided. The operation unit 31 is composed of a keyboard, a pointing device such as a mouse and a touch pad, and outputs an operation signal corresponding to these operations to the processing unit 33. The display unit 32 displays the result (analysis result) of the "analysis process" by the processing unit 33.

The processing unit 33 is an example of the “processing unit”, and the measured value data D1 in which the measured value is recorded is transmitted from the electrochemical measuring device 2 (measuring device main body 2b) and stored in the storage unit 34. Further, the processing unit 33 analyzes the state of the electrolytic plating solution Xa by analyzing the measured value data D1 transmitted from the electrochemical measuring device 2 according to the analysis program Dp, and causes the display unit 32 to display the analysis result. At the same time, analysis result data D2 to D4 in which the analysis results are recorded are generated and stored in the storage unit 34 (an example of "analysis processing"). In this case, in the electrolytic plating solution analysis system 1 of this example, the processing unit 33 performs N kinds of inclusions (various additives and electrolytic plating solution Xa) contained in the electrolytic plating solution Xa in the "analysis process". It is configured so that a process for specifying the concentration of impurities (such as impurities mixed in) can be executed.

The specific contents of this "analysis process" will be described in detail later, but in this example, "electroplating solution analyzer", "electroplating solution analysis method" and "electroplating solution analysis program". As an example, an inhibitor (additive A) and an accelerator (additive A) added to the electrolytic plating solution Xa as "N kinds of inclusions contained in the electrolytic plating solution" to facilitate understanding of the above. It is assumed that the concentration of N = 2 kinds of "containing substances" of the additive B) is specified. Further, in this example, as an example, among various parameters such as "current efficiency", "plating amount" and "peak current" specified based on the measured value data D1 in which the result of "measurement processing" is recorded. (As an example, "current efficiency" and "plating amount") are set as "analytical parameters (parameters that change according to the type of inclusions contained in the electrolytic plating solution Xa and the concentration thereof)". The process shall be executed.

In this case, "current efficiency" is a parameter indicating the ratio of the current that contributed to the precipitation of the metal when the metal contained in the electrolytic plating solution Xa or the like was deposited (plated) on the electrode surface of the working electrode 12. As an example, the amount of electricity at the time of metal elution (based on the current value of the current flowing between the counter electrode 13 and the working electrode 12 when the metal deposited on the working electrode 12 is eluted in the electrolytic plating solution Xa or the like. The specified amount of electricity) is divided by the amount of electricity at the time of precipitation (the amount of electricity specified based on the current value of the current flowing between the counter electrode 13 and the working electrode 12 when the metal is deposited on the working electrode 12). It is required by

Further, the "plating amount" is defined as the amount of metal contained in the electrolytic plating solution Xa or the like deposited (plated) on the electrode surface of the working electrode 12 over a specified time. The mass of the metal, for example, is the current value (current value) of the current flowing between the counter electrode 13 and the working electrode 12 when the metal deposited on the working electrode 12 is eluted with the electrolytic plating solution Xa or the like. (Amount of electricity specified based on). Further, the "peak current" is the current flowing between the counter electrode 13 and the working electrode 12 when the metal deposited on the working electrode 12 is eluted into the electrolytic plating solution Xa or the like while changing the electrode potential of the working electrode 12. Is specified based on what electrode potential the current value of is the maximum value.

The storage unit 34 is an example of the “storage unit” and stores the above-mentioned analysis program Dp and model formula data D0 for specifying the concentration of various inclusions contained in the electrolytic plating solution Xa. In this case, the model formula data D0 is an example of the "second data", and the "concentration" of the content whose concentration is to be specified among the various contents contained in the electrolytic plating solution Xa and " An "analytical model formula" showing the correlation with the "analytical parameters" is recorded.

Specifically, in the model formula data D0, "Y = β ₀ + β ₁ X ₁ + β ₂ X ₂ + ε (primary model formula)" and “Y = β ₀ + β ₁ X” are described as “model formulas for analysis”. ₁ + β ₂ X ₂ + β ₁₂ X ₁ X ₂ + ε (interaction model formula) ”and“ Y = β ₀ + β ₁ X ₁ + β ₂ X ₂ + β ₁₂ X ₁ X ₂ + β ₁₁ X ₁ ² + β ₂₂ X ₂ ² + ε (Secondary model formula) ”is recorded. In this case, "Y" in each of the above model formulas is a value of "analytical parameter" (in this example, a value of "current efficiency" and "plating amount"), and "X ₁ " is an inhibitor ( The concentration of the additive A), "X ₂ " is the concentration of the accelerator (additive B), and "β ₀ , β ₁ ..." is an arbitrary coefficient (β ₀ , β ₁ ...) specified in the preparation of the model formula. Parameter), and "ε" is a known "adjustment value (error)".

In this example, the model formula data D0 in which the above three types of model formulas are recorded as "a plurality of types of analytical model formulas showing the correlation between the concentration of each content and each analytical parameter" is used. Depending on the "container" for which the concentration is to be specified, model formula data D0 in which one or two of the above three types of model formulas are recorded as "model formulas for analysis" may be used, or "3". Model formula data D0 in which four or more model formulas including model formulas such as "next model formula", "fourth model formula", etc. are recorded as "analytical model formulas" can be used.

Further, the storage unit 34 records the measured value data D1 transmitted from the electrochemical measuring device 2 and the value of the "analytical parameter" specified by the processing unit 33 based on the measured value data D1 as described later. The analysis result data D2 and D3, and the analysis result data D4 in which the concentration of each identified content is recorded are stored. In this example, the analysis result data D2 generated by the processing unit 33 based on the measured value data D1 corresponds to the "first data" as described later, and the analysis result data D2 and the model described above are used. Together with the formula data D0, it corresponds to "concentration specification data".

In order to analyze the state of the electrolytic plating solution Xa in the plating solution tank (identify the concentrations of the inhibitor and the accelerator contained in the electrolytic plating solution Xa) by the electrolytic plating solution analysis system 1, first, FIG. Samples Xb1 to Xb9 shown in the above are prepared. In this case, the samples Xb1 to Xb9 correspond to "a plurality of types of samples containing the same metal ions as the electrolytic plating solution and having different combinations of concentrations of each content", and in this example, the concentration is used as an example. The "impurities (inhibitors and accelerators in this example)" to be specified are not plated with a new electroplating solution Xa (the electrolytic plating solution Xa), and the inhibitors, accelerators, etc. It is manufactured by adding it to the electrolytic plating solution Xa) to which the above additives are not added or impurities are not mixed.

Specifically, as shown in FIG. 2, in this example, the amount of the inhibitor added is appropriate, the amount of the inhibitor added is insufficient, and the amount of the inhibitor added is excessive. 3 x 3 = 9 types depending on the combination of one state, the state where the amount of the accelerator added is appropriate, the state where the amount of the accelerator added is insufficient, and the state where the amount of the accelerator added is excessive. Samples Xb1 to Xb9 (hereinafter, also referred to as "sample Xb" when not distinguished) are produced.

In this case, in this example in which a model formula including an "interaction model formula" and a "secondary model formula" as the "analytical model formula" is used in the "analysis process" described later, the amount (concentration) of the inhibitor added. It is preferable that the number of types of the accelerator and the number of types of the amount (concentration) of the accelerator added are 3 or more, respectively. Further, in this example in which the concentration of the inhibitor or accelerator whose addition amount (concentration) should be appropriate is specified as the "containing material", one of the three states of the addition amount of each of the above "contents" is specified. It is preferable that one is "appropriate amount" and the other two are "insufficient (less than appropriate amount)" and "excessive (more than appropriate amount)".

Next, the "measurement process" for each of the above samples Xb is executed. Specifically, first, the electrodes 11 to 13 are attached to the casing 10 to assemble the electrochemical sensor 2a, and the electrochemical sensor 2a is connected to the measuring device main body 2b via the signal cable 2c. Subsequently, after immersing the electrode surfaces of the electrodes 11 to 13 of the electrochemical sensor 2a in the sample Xb, the operation unit 21 of the measuring device main body 2b is operated to instruct the start of the “measurement process”. In response to this, the processing unit 23 starts the “measurement process” to generate the measured value data D1, and stores the generated measured value data D1 in the storage unit 24. At this time, as an example, the processing unit 23 has a reduction potential (the electrode surface of the working electrode 12) within a sufficiently wide potential range centered on the reduction potential during the actual plating process using the electrolytic plating solution Xa to be analyzed. The "measurement process" is executed a plurality of times by changing the electrode potential when the metal is deposited on the metal.

As an example, this "measurement process" is the same as the procedure of "measurement value acquisition process" in the analysis method disclosed by the applicant in JP-A-2016-105072 and JP-A-2016-105073. It can be carried out by the procedure. Therefore, detailed description of the same matters as those disclosed in these publications will be omitted. By executing such a "measurement process" for each sample Xb, the measurement value data D1 in which the measurement results of the "measurement process" executed at each of a plurality of types of reduction potentials for the sample Xb1 are recorded. Therefore, a plurality of measurement value data D1 up to the measurement value data D1 in which the measurement results of the "measurement processing" executed at each of the plurality of types of reduction potentials of the sample Xb9 are recorded are stored in the storage unit 24.

Next, the electrochemical sensor 2a is pulled up from the sample Xb, and if necessary, the electrodes 11 to 13 are removed from the casing 10 and housed in a storage case, and then the measuring device main body is passed through the signal cable 4 (see FIG. 1). 2b is connected to the analyzer 3. Subsequently, by operating the operation unit 21 of the electrochemical measurement device 2 (measurement device main body 2b), each measurement value data D1 stored in the storage unit 24 is transmitted to the analyzer 3.

In response to this, in the analyzer 3, the processing unit 33 stores each measured value data D1 transmitted from the electrochemical measuring device 2 in the storage unit 34. The transmission of the measured value data D1 from the electrochemical measurement device 2 to the analyzer 3 is not limited to the above example of operating the operation unit 21 of the electrochemical measurement device 2, and the operation unit 31 of the analyzer 3 is used. By operating and transmitting a transmission request signal from the analyzer 3 to the electrochemical measuring device 2, the electrochemical measuring device 2 can transmit the measured value data D1 to the analyzer 3. As described above, the measured value data D1 required for the analysis of each sample Xb is stored in the storage unit 34 of the analyzer 3.

Next, the analyzer 3 executes an "analytical process" for acquiring "analytical parameters" for each sample Xb. As an example, this "analytical process" can be carried out in the same procedure as the "analytical process" disclosed by the applicant in the above-mentioned publication. At this time, in this example, the processing unit 33 sets two parameters of "current efficiency" and "plating amount" as "analytical parameters" for each sample Xb in M types (M is a natural number of 2 or more). : As an example, each reduction potential of -0.30V, -0.25V, -0.20V, -0.15V, -0.10V, -0.05V and 0.00V (M = 7 types) Identify. As a result, as shown in FIG. 3, the reduction potentials V1, V2 ... VM for the sample Xb1 (for example, seven types of reduction potentials having a reduction potential V1 of −0.30V and a reduction potential VM of 0.00V). From the current efficiencies A11, A12 ... A1M and the plating amounts B11, B12 ... B1M based on the measured value data D1 of the "measurement process" executed in, the reduction potentials V1, V2 ... VM for the sample Xb9 were executed. The current efficiencies A91, A92 ... A9M and the plating amounts B91, B92 ... B9M based on the measured value data D1 of the "measurement process" are specified, respectively.

Subsequently, the processing unit 33 sets each of the above-mentioned "current efficiency" and each "plating amount" specified according to the analysis program Dp, the concentration of the inhibitor or accelerator in the corresponding sample Xb, and the corresponding measured value data. The analysis result data D2 is generated in association with the reduction potential at the time of acquisition of D1, and the generated analysis result data D2 is stored in the storage unit 34 as "first data". Regarding the above analysis result data D2 (first data), unless the type of the electrolytic plating solution Xa to be analyzed and the type of the electrochemical sensor 2a (each electrode 11 to 13) used are changed. It can be used continuously. Therefore, the work of acquiring the analysis result data D2 may be performed only once at an arbitrary location for each combination of the electrolytic plating solution Xa to be analyzed and the electrochemical sensor 2a to be used.

Next, the processing unit 33 executes the "first process" according to the analysis program Dp. In this case, in the electrolytic plating solution analysis system 1 (analyzer 3) of this example, any model formula among the model formulas stored in the model formula data D0 is suitable for specifying the concentration of the inhibitor or accelerator. The process of identifying the model formula and the model formula to which the "analytical parameters" corresponding to the reduction potential are substituted are the model formulas suitable for specifying the concentrations of the inhibitor and the accelerator. The process to be performed is executed in this order as the "first process".

Specifically, the processing unit 33 first, at the time of "measurement processing", executed the value of each "analysis parameter" in the analysis result data D2 and the value indicating the concentration of each "content" for each sample Xb. For each reduction potential of, the "first model formula" is generated by substituting each "model formula for analysis" in the model formula data D0. At this time, as an example, the processing unit 33 generates a "first model formula" by applying each of the above values to the model formula by the method of least squares.

Subsequently, the processing unit 33 has the "first model formula" ("predetermined in advance") in which the difference from each value recorded in the analysis result data D2 is the smallest among the generated "first model formulas". An example of "a first model formula of a kind satisfying the second criterion") is specified for each "content". Specifically, the processing unit 33 substitutes the concentration of the inhibitor in each sample Xb associated with each “analytical parameter” in the analysis result data D2 into the primary model formula in the model formula data D0, respectively. "1 model formula", "first model formula" in which the concentration of the inhibitor in each sample Xb is substituted into the interaction model formula, and "1 model formula" in which the concentration of the inhibitor in each sample Xb is substituted into the secondary model formula, respectively. Among the "first model formulas", the "first model formula" having the smallest R-squared value (determination coefficient) is specified as the "first model formula satisfying the second criterion".

As a result, any one of the "primary model formula", the "interaction model formula" and the "secondary model formula" among the various "first model formulas" is suitable for the analysis of the inhibitor. It is specified as a model formula (first model formula). Further, the processing unit 33 also specifies a model formula (first model formula) suitable for analysis of the accelerator as the “containing material” in the same manner as the specification of the model formula for the inhibitor.

Next, in the processing unit 33, among the "first model formulas" for each "content" specified in the above processing, the "first model formula" to which any reduction potential is substituted is each "container". Is suitable for specifying the concentration of "". Specifically, the processing unit 33 sets the term "β _n " to be multiplied by the term "X ₁ " (concentration of inhibitor) in each "first model formula" to which each reduction potential is applied as "0". The p-value at the time of each calculation was obtained, and the model formula in which the obtained p-value was the smallest (an example of "a first model formula satisfying a predetermined first criterion": with respect to "X ₁ " which is the concentration of the inhibitor The model formula having the greatest influence) is specified as the "first model formula" of the reduction potential suitable for specifying the concentration of the inhibitor. Similarly, the processing unit 33 sets the term "β _n " to be multiplied by the term "X ₂ " (concentration of the accelerator) in each "first model formula" to which each reduction potential is applied to be "0". Each p-value is obtained, and the model formula with the smallest p-value (an example of "a first model formula satisfying a predetermined first criterion": influence on "X ₂ ", which is the concentration of the accelerator. Is specified as the "first model formula" of the reduction potential suitable for specifying the concentration of the accelerator.

As described above, the "first process" is completed, and any of the "primary model formula", "interaction model formula" and "secondary model formula" is suitable for specifying the concentration of the inhibitor. Matters of whether or not it is preferable to execute the "measurement process" at which reduction potential when specifying the concentration of the inhibitor, "primary model formula", "interaction model formula" and "secondary model formula" Which model formula is suitable for specifying the concentration of the accelerator, and at which reduction potential it is preferable to execute the "measurement process" when specifying the concentration of the accelerator. Will be done.

Regarding the specific items in this "first treatment", the type of electrolytic plating solution Xa to be analyzed (that is, the type of sample Xb), the type of model formula of model formula data D0, and the electrochemical used. As long as the type of the sensor 2a (each electrode 11 to 13) does not change, it can be used continuously. Therefore, the work of acquiring the analysis result data D2 may be performed only once at an arbitrary place for each combination of the electrolytic plating solution Xa to be analyzed, the model formula to be used, and the electrochemical sensor 2a to be used. As described above, the preparation for the substantial "analytical process" of the electrolytic plating solution Xa in the plating solution tank is completed.

Next, a "measurement process" for the electrolytic plating solution Xa in the plating solution tank is executed. At this time, by operating the operation unit 21 of the electrochemical measuring device 2, the reduction associated with the N = 2 "first model formulas" specified in the above "first process". Set the measurement conditions so that the reduction treatment is performed at the potentials (the reduction potential identified as suitable for specifying the concentration of the inhibitor and the reduction potential identified as suitable for specifying the concentration of the accelerator). .. Next, after immersing the electrode surfaces of the electrodes 11 to 13 of the electrochemical sensor 2a in the electrolytic plating solution Xa to be analyzed, the operation unit 21 of the measuring device main body 2b is operated to start the "measurement process". Instruct. In response to this, the processing unit 23 starts the “measurement process” to generate the measured value data D1, and stores the generated measured value data D1 in the storage unit 24.

Next, the electrochemical sensor 2a is pulled up from the electrolytic plating solution Xa, and if necessary, the electrodes 11 to 13 are removed from the casing 10 and housed in a storage case, and then the measuring device main body 2b is analyzed via the signal cable 4. Connect to device 3. Subsequently, as an example, by operating the operation unit 21 of the electrochemical measurement device 2 (measurement device main body 2b), each measurement value data D1 stored in the storage unit 24 is transmitted to the analyzer 3.

In response to this, in the analyzer 3, the processing unit 33 starts the “second processing” according to the analysis program Dp. In this "second process", the process unit 33 first stores each measured value data D1 for the electrolytic plating solution Xa transmitted from the electrochemical measuring device 2 in the storage unit 34. As a result, the measured value data D1 required for the analysis of the electrolytic plating solution Xa is stored in the storage unit 34 of the analyzer 3 (“Associated with the N first model formulas specified by the first process”. An example of the process of "acquiring the measurement result of the electrochemical measurement process performed on the electrolytic plating solution at the reduced potential").

Next, the processing unit 33 executes an "analytical process" based on the measured value data D1 for the electrolytic plating solution Xa. At this time, in this example, the processing unit 33 specifies two parameters of "current efficiency" and "plating amount" as "analytical parameters". Subsequently, the processing unit 33 associates the specified "current efficiency" and "plating amount" with the reduction potential at the time of acquisition of the corresponding measured value data D1 to generate the analysis result data D3 and stores it in the storage unit 34. ..

Next, the processing unit 33 sets the values of each “analysis parameter” in the analysis result data D3 and the value of the reduction potential associated with those values to each “container” in the above-mentioned “first processing”. A "second model formula" is generated by substituting into the "analysis model formula" corresponding to N = 2 "first model formulas" specified for each case. Further, the processing unit 33 obtains and obtains "X ₁ (concentration of inhibitor)" and "X ₂ (concentration of accelerator)" by solving the simultaneous equations of each generated "second model formula". The value is stored in the storage unit 34 as the analysis result data D4.

As described above, the "second treatment" is completed, and the concentration of the inhibitor and the concentration of the accelerator contained in the electrolytic plating solution Xa (electroplating solution Xa to be analyzed) in the plating solution tank are specified. To do. As a result, the value of the analysis result data D3 (concentration of the inhibitor and the concentration of the accelerator) is displayed on the display unit 32, and the analysis work for the electrolytic plating solution Xa is completed.

As described above, in this electrolytic plating solution analysis system 1 and its electrolytic plating solution analysis method, the measurement results of the "electrochemical measurement process" executed for each of a plurality of types of samples Xb at a plurality of types of reduction potentials are recorded. Multiple types of "analytical parameters (in this example," current efficiency "and" plating amount ")" for each reduction potential specified for each sample Xb based on the measured value data D1 are the values of each sample. Each "analysis" in the analysis result data D2 (first data) recorded in association with the concentration and reduction potential values of each "content (in this example," suppressor "and" accelerator ")" in Xb. The value of the "parameter" and the value indicating the concentration of each "content" are defined in advance for each reduction potential of each sample Xb, indicating the correlation between the concentration of each "content" and each "parameter for analysis". From among the plurality of "first model formulas" substituted for each "model formula for analysis (model formula recorded in model formula data D0 (second data))", for each "content", Electrochemical plating at the reduction potentials associated with the "first process" that identifies the "first model equation" that meets the pre-defined first criteria and the specified N "first model equations". Along with acquiring measurement value data D1 in which the measurement results of the "electrochemical measurement process" executed for the liquid Xa are recorded, a plurality of types of "analytical parameters" specified based on the acquired measurement value data D1. Based on each "second model formula" in which the value of is substituted into the "analytical model formula" corresponding to the above N "first model formulas", N kinds of "containing substances" in the electrolytic plating solution Xa A "second process" for specifying the concentration of each of the above is executed. Further, in this analysis program Dp, the processing unit 33 in the electrolytic plating solution analysis system 1 executes the above-mentioned "first processing" and "second processing".

Therefore, according to the electrolytic plating solution analysis system 1, the electrolytic plating solution analysis method, and the analysis program Dp, N types (N = 2 types in the above example) of "containing substances" contained in the electrolytic plating solution Xa. Since the concentration of "" can be specified in one operation, the concentration of each "content" for the electrolytic plating solution Xa, which often contains multiple types of "containing", can be determined in a short time. Can be identified. Further, by executing the "first treatment" once, when the concentration of each "containing material" contained in the electrolytic plating solution Xa should be specified, only the "second treatment" should be executed. Since the analysis result (concentration of the "containing material") can be obtained in the above, the state of the electrolytic plating solution Xa can be sequentially grasped, and the object can be plated under suitable conditions.

Further, in the electrolytic plating solution analysis system 1 and the electrolytic plating solution analysis method thereof, in the "first process", a plurality of types of "first" corresponding to the plurality of types of "analytical model formulas" in the model formula data D0. From the "model formulas of", the type of "first model formula" that satisfies the second predetermined criterion is specified, and from each of the specified "first model formulas", each "container" For each, a "first model formula" that satisfies the first criterion is specified. Further, in this analysis program Dp, in the "first process", the process unit 33 in the electrolytic plating solution analysis system 1 is made to execute the above process.

Therefore, according to the electroplating solution analysis system 1, the electroplating solution analysis method, and the analysis program Dp, a plurality of types of "analytical model formulas" are prepared according to the characteristics of the "containing material" whose concentration should be specified. By doing so, the concentrations of various "containing substances" can be accurately specified.

Further, in the electrolytic plating solution analysis system 1, the processing unit 33 of the analyzer 3 analyzes based on the measurement result of the "electrochemical measurement process" for each reduction potential of each sample Xb by the electrochemical measurement device 2. The result data D2 is generated and stored in the storage unit 34, and in the "second process", a plurality of result data D2 are generated based on the measurement results of the "electrochemical measurement process" for the electrolytic plating solution Xa by the electrochemical measuring device 2. Specify the value of the type of "analytical parameter" to specify the concentration of each "content". Therefore, according to this electrolytic plating solution analysis system 1, each "content" contained in the electrolytic plating solution Xa is not provided with an electrochemical measuring device separately from the electrolytic plating solution analysis system 1 (electrolytic plating solution analyzer). The concentration of "" can be preferably specified.

The configuration of the "electroplating solution analyzer", the specific contents of the "electroplating solution analysis method", and the processing procedure of the "electroplating solution analysis program" are described in the configuration of the above-mentioned electroplating solution analysis system 1. , The electroplating solution analysis method by the electroplating solution analysis system 1, and the processing procedure of the analysis program Dp are not limited to the examples. For example, in the "electrochemical measurement process", the configuration, method, and procedure for executing the "tripolar measurement" using the reference electrode 11, the working electrode 12, and the counter electrode 13 have been described as an example. -Instead of the method / procedure, a configuration / method / procedure for performing "bipolar measurement" using the reference electrode 11 and the working electrode 12 can be adopted.

Further, although an example of specifying the concentration of N = 2 types of "containing matter" has been described, a configuration / method / procedure for specifying the concentration of N = 3 or more types of "containing matter" can also be adopted. Further, the "containing material" is not limited to the "additives" that should be added to the electrolytic plating solution Xa, and various "foreign substances (for example, the plating solution tank, etc.) that may be mixed in the electrolytic plating solution Xa are washed. It is also possible to specify the concentration of the "cleaning liquid" used in the case or the "lubricator") adhering to the surface of the object to be plated as the "containing material".

Further, the "sample" is not limited to a new electrolytic plating solution Xa to which a "concentration" to be specified is added, and the concentration is specified to an electrolytic solution containing the same metal ions as the electrolytic plating solution Xa to be analyzed. A liquid containing the target "containing material" can be used. In addition, as a "combination of concentrations of each content", sample Xb is prepared by combining three amounts of "content" as "appropriate amount", "content" as "insufficient", and "content" as "excess". An example of production has been described, but instead of such a "sample", for example, "concentration" is "significantly insufficient", "concentration" is "slightly insufficient", and "concentration" is "appropriate amount". A combination of amounts such as "sample" produced by a combination of such amounts, "concentration" is "significantly excessive", "concentration" is "slightly excessive", and "concentration" is "appropriate amount". You can also use the "sample" made in.

Further, an example in which an "electrochemical measurement process" for each sample Xb is executed and "analytical parameters for each reduction potential of each sample" are specified based on the measured value data D1 in which the measurement results are recorded. However, regarding the "measurement result" for specifying the "analytical parameter for each reduction potential of each sample", the "electrochemical measurement process" performed separately from the "analytical process" in the present invention. "Measurement result" can be used. Further, prior to the "second treatment", the "electrochemical measurement process" for the electrolytic plating solution Xa to be analyzed is executed, and the "electrochemical plating solution" is performed based on the measured value data D1 in which the measurement results are recorded. Although an example of specifying the "analytical parameter" has been described, the "measurement result" for specifying the "analytical parameter" is also "electrochemistry" executed separately from the "analytical process" in the present invention. "Measurement result" of "Measurement process" can be used. When these configurations and methods are adopted, the "measuring unit" can be excluded from the constituent requirements of the "electroplating solution analyzer".

Further, in the "first process", the difference from each value recorded in the analysis result data D2 is the model formula having the smallest R-squared value (coefficient of determination) among the "first model formulas". The configuration, method, and procedure for specifying (the smallest model formula) as "a first model formula of a type that satisfies a predetermined second criterion" have been described as an example, but the R-squared value (coefficient of determination) is It is also possible to adopt a configuration, method, or procedure that specifies the second smallest model formula or the third smallest model formula as "a first model formula of a type that satisfies the second criterion".

Further, in the "first process", the p value when the term "β _n " multiplied by the term "X ₁ " (concentration of inhibitor) in each "first model formula" is set to "0" is The smallest model formula (the model formula that has the greatest effect on "X ₁ ") and the "β _n " term that is multiplied by the "X ₂ " term (accelerator concentration) in each "first model formula" are "β _n ". A configuration / method for specifying a model formula having the smallest p-value when "0" is set (a model formula having the greatest effect on "X ₂ ") as a "first model formula satisfying a predetermined first criterion". -Although the procedure was explained as an example, the configuration, method, and procedure for specifying the model formula with the second smallest p value and the model formula with the third smallest p value as the "first model formula satisfying the first criterion" are described. It can also be adopted.

In addition, an electrolytic plating solution in which an electrochemical measuring device 2 that executes an "electrochemical measurement process" and an analyzer 3 that executes an "analytical process (first process and second process)" are separately configured. Although the analysis system 1 has been described as an example, "electrolysis" is performed using an "electroplating solution analyzer" (not shown) in which the electrochemical measuring device 2 and the analyzer 3 are integrated in the electrolytic plating solution analysis system 1. It is also possible to perform analysis of the electrolytic plating solution Xa by the "plating solution analysis method".

1 Electrolytic plating solution analysis system 2 Electrochemical measuring device 2a Electrochemical sensor 2b Measuring device main body 2c Signal cable 3 Analytical device 4 Signal cable 14 Signal processing circuit board 21, 31 Operation unit 22, 32 Display unit 23, 33 Processing unit 24, 34 Storage unit D0 Model formula data D1 Measured value data D2 Analysis result data D3 Analysis result data D4 Analysis result data Dp Analysis program Xa Electrolytic plating solution Xb1 to Xb9 Sample

Claims (7)

A processing unit that executes an analysis process that analyzes the state of the electrolytic plating solution based on the measurement results of the electrochemical measurement process that targets the electrolytic plating solution to be analyzed.
It is provided with a storage unit for storing concentration specifying data for specifying the concentration of N kinds (N is a natural number of 2 or more) contained in the electrolytic plating solution.
As the concentration identification data, the storage unit targets a plurality of types of samples containing the same metal ions as the electrolytic plating solution and having different combinations of concentrations of the respective inclusions at a plurality of types of reduction potentials. The values of a plurality of types of analytical parameters for each reduction potential specified for each sample based on the measurement results of the electrochemical measurement process performed are the concentration of each content in each sample and the reduction. The first data recorded in association with the potential value and the second data of the predetermined analytical model formula showing the correlation between the concentration of each of the inclusions and the respective analytical parameters are stored. ,
In the analysis process, the processing unit sets the value of each analysis parameter in the first data and the value indicating the concentration of each content in the second data for each reduction potential of each sample. A first process for identifying the first model formula that satisfies the first predetermined criterion for each of the inclusions from the plurality of first model formulas substituted into the analytical model formulas. And, the measurement result of the electrochemical measurement process executed for the electrolytic plating solution at the reduction potential associated with the N first model formulas specified by the first process is acquired. , Based on each second model formula in which the values of the plurality of types of analytical parameters specified based on the acquired measurement results are substituted into the analytical model formulas corresponding to the N first model formulas. , An electrolytic plating solution analyzer that executes a second treatment for specifying the concentration of each of the inclusions in the electrolytic plating solution. The storage unit stores, as the second data, a plurality of types of the analysis model formulas showing the correlation between the concentration of each content and the analysis parameters.
In the first process, the processing unit is of a type that satisfies a predetermined second criterion from among a plurality of types of the first model formulas corresponding to the plurality of types of analytical model formulas. The electrolysis according to claim 1, wherein the model formula of 1 is specified, and the first model formula satisfying the first criterion is specified for each of the contained substances from the specified first model formulas. Plating liquid analyzer. A measuring unit for executing the electrochemical measurement process for the electrolytic plating solution and each sample is provided.
The processing unit generates the first data based on the measurement result of the electrochemical measurement process for each reduction potential of each sample of the measuring unit, stores the first data in the storage unit, and stores the first data in the storage unit. In the second process, the values of the plurality of types of analytical parameters are specified based on the measurement results of the electrochemical measurement process for the electrolytic plating solution by the measuring unit, and the concentration of each of the inclusions is specified. The electrolytic plating solution analyzer according to claim 1 or 2. To identify the measurement result of the electrochemical measurement process for the electrolytic plating solution to be analyzed and the concentration of N types (N is a natural number of 2 or more) contained in the electrolytic plating solution. In the analysis process for analyzing the state of the electrolytic plating solution based on the concentration specifying data, the concentration specifying data contains the same metal ions as the electrolytic plating solution and the combination of the concentrations of the respective inclusions is mutual. Multiple types of analytical parameters for each reduction potential specified for each sample based on the measurement results of the electrochemical measurement process executed at a plurality of types of reduction potentials for a plurality of different types of samples. The value of each analytical parameter in the first data recorded in association with the concentration of each content in each sample and the value of the reduction potential, and the value indicating the concentration of each content. For each reduction potential of each sample, substitute into the analysis model formula in the second data of the predetermined analysis model formula showing the correlation between the concentration of each content and each analysis parameter. From the plurality of first model formulas, the first process for specifying the first model formula satisfying the first predetermined criterion for each content and the first process are performed. The measurement results of the electrochemical measurement process performed on the electrolytic plating solution at the reduction potentials associated with the specified N first model formulas are acquired, and based on the acquired measurement results. Based on each of the second model formulas in which the values of the plurality of types of analytical parameters specified in the above are substituted into the analytical model formulas corresponding to the N first model formulas, each of the above in the electrolytic plating solution. An electrolytic plating solution analysis method for performing a second treatment for specifying the concentration of each of the inclusions. In the first process, among the plurality of types of the first model formulas corresponding to the plurality of types of the analysis model formulas in the second data, the type that satisfies the predetermined second criterion. The fourth aspect of claim 4, wherein the first model formula is specified, and the first model formula satisfying the first criterion is specified for each of the contents from the specified first model formulas. Electroplating solution analysis method. A processing unit that executes an analysis process that analyzes the state of the electrolytic plating solution based on the measurement results of the electrochemical measurement process that targets the electrolytic plating solution to be analyzed, and N types (N types) contained in the electrolytic plating solution. N is an electrolysis in which the processing unit in an electroplating solution analyzer provided with a storage unit for storing concentration-specific data for specifying the concentration of two or more natural numbers) is made to perform the analysis process. It is a program for plating solution analysis.
As the concentration identification data, the storage unit contains the same metal ions as the electrolytic plating solution, and a plurality of types of samples having different combinations of concentrations of the respective contents are targeted at a plurality of types of reduction potentials, respectively. The values of a plurality of types of analytical parameters for each reduction potential specified for each sample based on the measurement results of the performed electrochemical measurement process are the concentration of each content in each sample and the reduction. The first data recorded in association with the value of the potential and the second data of the predetermined analytical model formula showing the correlation between the concentration of each of the inclusions and the parameters for each analysis are stored. In this state, in the analysis process, the value of each analysis parameter and the value indicating the concentration of each of the inclusions in the first data are given to the processing unit for each reduction potential of the sample. Among the plurality of first model formulas substituted into the analytical model formulas in the second data, the first model formula satisfying a predetermined first criterion for each of the inclusions. The electrochemical measurement process performed on the electrolytic plating solution at the reduction potential associated with the N first model formulas specified by the first process and the first process for specifying the above. The measurement results of the above are acquired, and the values of the plurality of types of analysis parameters specified based on the acquired measurement results are substituted into the analysis model equations corresponding to the N first model equations. An electrolytic plating solution analysis program for executing a second process for specifying the concentration of each of the inclusions in the electrolytic plating solution based on the second model formula. In a state where, as the second data, a plurality of types of the analysis model formulas showing the correlation between the concentration of each content and the analysis parameters are stored in the storage unit, the processing unit is stored. In the first process, among the plurality of types of the first model formulas corresponding to the plurality of types of analytical model formulas, the first model of a type satisfying a predetermined second criterion. The sixth aspect of claim 6, wherein a process of specifying the first model formula that satisfies the first criterion is executed for each of the inclusions from the specified first model formulas. Electrolytic plating solution analysis program.

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