On-line analysis instrument for cobalt-plated inorganic matter and organic matter

Abstract

The embodiment of the invention provides an online analysis instrument for cobalt-plated inorganic matter and organic matter, and relates to the field of cobalt-plated detection. The cobalt-plated inorganic matter and organic matter online analysis instrument comprises a PLC control terminal and a test case, an analysis chamber and a sampling chamber are formed in the upper end and the lower end of an inner cavity of the test case respectively, an analysis and test module is integrally installed in an inner cavity of the analysis chamber, and a sampling module is integrally installed in an inner cavity of the sampling chamber; the analysis test module comprises a colorimetric analysis unit, a titrimetric analysis unit and a CVS analysis unit which are matched for use and are used for accurately analyzing the bath solution; meanwhile, the sampling module comprises a first sampling unit and a second sampling unit. The device provides a cobalt plating inorganic matter and organic matter on-line analysis instrument, and the concentration of boric acid, cobalt ions and inhibitor additives in the electroplating liquid can be accurately measured, so that the metallization process in semiconductor manufacturing is optimized.

Description

Technical Field

[0001] The present application relates to the technical field of cobalt plating detection, and in particular to an online analysis instrument for cobalt plating inorganic and organic substances. Background Art

[0002] In the semiconductor industry, the manufacturing process of silicon chips involves a multi-step precision process. Among them, the metallization process is a key link, usually by depositing a metal layer on a silicon wafer to form electrodes and wires. In this process, cobalt plating technology is widely used in copper interconnect intermediate layers to enhance electromigration resistance and reduce resistance. At the same time, additives such as boric acid and cobalt ions play an important role in the cobalt plating process. They can adjust the properties of the plating solution and improve the uniformity and performance of the coating. Therefore, the development of an efficient cobalt plating analyzer to accurately determine the concentration of boric acid, cobalt ions and inhibitor additives is of great significance for optimizing the cobalt plating process and improving the performance of semiconductor devices.

[0003] In the electroplating process, boric acid is used as a buffer to maintain the pH stability of the electroplating solution. It can effectively prevent the acidification of the electroplating solution caused by the generation of hydrogen ions during the electrolysis reaction, thereby ensuring the smooth progress of the electroplating process. In addition, boric acid can also increase the conductivity of the electroplating solution, improve electroplating efficiency and coating quality. By maintaining a suitable pH environment, boric acid helps to form a dense, uniform and non-porous coating.

[0004] Cobalt ions are the main component of the cobalt layer formed during the electroplating process. It is reduced in the electrolytic reaction and deposited on the surface of the substrate to form a dense metallic cobalt coating. Cobalt coatings have excellent hardness, wear resistance and corrosion resistance, so they are widely used in many demanding applications. The concentration of cobalt ions has a direct impact on the structure and properties of the coating, and optimizing the concentration of cobalt ions helps to obtain the desired coating characteristics.

[0005] Inhibitor additives play a key regulatory role in the electroplating process. They control the growth rate and uniformity of the coating by adsorbing on the substrate surface and inhibiting the reduction of metal ions in local areas. These additives can prevent the formation of dendrites, reduce porosity and defects in the coating, and improve the smoothness and consistency of the coating. Different types of inhibitor additives can adjust the physical and chemical properties of the coating as needed to meet the needs of specific applications.

[0006] Therefore, developing an efficient cobalt plating analyzer that can accurately measure the concentration of boric acid, cobalt ions and inhibitor additives is of great significance for optimizing the cobalt plating process and improving the performance of semiconductor devices. The technical background and innovation of this patent are based on these key needs, aiming to provide an effective solution to ensure the precise control of each component in the electroplating process and ensure the high quality of the final product. Summary of the invention

[0007] The present application aims to solve at least one of the technical problems existing in the prior art. To this end, the present application proposes an online analyzer for inorganic and organic cobalt plating, which aims to accurately determine the concentration of boric acid, cobalt ions and inhibitor additives in the electroplating solution to optimize the metallization process in semiconductor manufacturing. The analyzer can ensure pH stability and good conductivity during the electroplating process, and effectively control the uniformity and performance of the coating, thereby improving the hardness, wear resistance and corrosion resistance of the cobalt plating layer, reducing defects and pores, and ultimately improving the overall performance and reliability of semiconductor devices.

[0008] According to the embodiment of the present application, the cobalt-plated inorganic and organic online analyzer comprises: a PLC control terminal, and a test chassis for controlling the online analyzer, wherein the upper and lower ends of the inner cavity of the test chassis are respectively provided with an analysis chamber and a sampling chamber, wherein the inner cavity of the analysis chamber is integrated with an analysis and test module, and the inner cavity of the sampling chamber is integrated with a sampling module; The analysis and testing module includes a colorimetric analysis unit, a titration analysis unit, and a CVS analysis unit, which are used together to accurately analyze the tank liquid; At the same time, the sampling module includes sampling unit 1 and sampling unit 2. Sampling unit 1 is used for sampling and analyzing the colorimetric analysis unit and the titration analysis unit, while sampling unit 2 is used for liquid supply analysis of the CVS analysis unit.

[0009] According to some embodiments of the present application, the sampling unit 1 includes a sampling pump 1, a defoaming channel 1 and a tank liquid chamber 1, wherein the tank liquid chamber 1 is used to store the tank liquid, and the output end of the tank liquid chamber 1 and the input end of the sampling pump 1 are connected by a pipeline. At the same time, the output end of the sampling pump 1 and the input end of the defoaming channel 1 are connected by a pipeline, and the output end of the defoaming channel 1 and the input end of the tank liquid chamber 1 are connected to each other.

[0010] According to some embodiments of the present application, the sampling unit 2 includes a sampling pump 2, a defoaming channel 2 and a tank liquid chamber 2, wherein the tank liquid chamber 2 is used to store the tank liquid, and the output end of the tank liquid chamber 2 and the input end of the sampling pump 2 are connected through a pipeline. At the same time, the output end of the sampling pump 2 and the input end of the defoaming channel 2 are connected through a pipeline, and the output end of the defoaming channel 2 and the input end of the tank liquid chamber 2 are connected to each other.

[0011] According to some embodiments of the present application, liquid supply is increased between the analysis and testing module and the sampling module via a multi-channel liquid supply valve group, and the multi-channel liquid supply valve group includes a multi-channel valve one and a multi-channel valve two, wherein the output end of the multi-channel valve one is connected to a sampling pump three, and the output end of the multi-channel valve two is connected to a sampling pump eight.

[0012] According to some embodiments of the present application, the multi-channel liquid supply valve group also includes a standard sample section and a pure water section one, wherein the standard sample section and the pure water section one are two groups, the standard sample section is used to store solution standards, and the pure water section one is used to store pure water.

[0013] According to some embodiments of the present application, the input end of the colorimetric analysis unit is connected to a sampling pump 4 through a pipeline, and the input end of the sampling pump 4 is connected to a standard solution portion through a pipeline; The colorimetric analysis unit is connected to a cleaning and waste discharge part 1 through a pipeline, and a solenoid valve 1 is installed on the pipeline between the cleaning and waste discharge part 1 and the colorimetric analysis unit.

[0014] According to some embodiments of the present application, the input end of the titration analysis unit is connected to a sampling pump 7 through a pipeline, and the input end of the sampling pump 7 is connected to a titration standard liquid portion through a pipeline; The titration analysis unit is connected to a second cleaning and draining part through a pipeline, and a second solenoid valve is installed on the pipeline between the second cleaning and draining part and the titration analysis unit; The input end of the titration analysis unit is also connected to a sampling pump 6 through a pipeline, wherein the input end of the sampling pump 6 and the output end of the auxiliary reagent part are connected to each other through a pipeline.

[0015] According to some embodiments of the present application, the colorimetric analysis unit and the titration analysis unit are both connected to a sampling pump five through pipelines, and the input end of the sampling pump five is connected to the pure water part two, and the output end of the sampling pump five is respectively connected to the colorimetric analysis unit and the titration analysis unit through pipelines.

[0016] According to some embodiments of the present application, the CVS analysis unit is connected to the pure water part three and the VMS storage part through pipelines, wherein the output end of the pure water part three is connected to the sampling pump nine through a pipeline, and the output end of the VMS storage part is connected to the sampling pump ten through a pipeline.

[0017] According to some embodiments of the present application, the CVS analysis unit is connected to the cleaning and waste discharge part three through a pipeline, and a solenoid valve three is installed on the pipeline on the surface of the cleaning and waste discharge part three, and the solenoid valve three is used to control the on-off of the pipeline on the cleaning and waste discharge part three.

[0018] The beneficial effects of the present application are as follows: the device ensures the stability and consistency of the coating quality by accurately measuring the concentrations of boric acid, cobalt ions and inhibitor additives in the electroplating solution; the real-time monitoring and analysis capabilities greatly improve production efficiency and reduce tedious sample preparation and long testing processes; automated operations reduce dependence on professionals, reduce operational difficulty and the risk of errors; real-time monitoring capabilities ensure that process problems can be quickly discovered and corrected, significantly reducing production costs; its high sensitivity can detect slight changes in low-concentration components, ensuring the uniformity and performance of the coating.

[0019] These advantages make the on-line analyzer of inorganic and organic substances in cobalt plating an ideal choice for optimizing electroplating processes and improving product quality. The on-line analyzer of inorganic and organic substances in cobalt plating can complete these measurements in real time and efficiently, significantly improving production efficiency and process control accuracy.

[0020] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments of the present application will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0022] Figure 1 It is a three-dimensional schematic diagram of the overall structure of the on-line analyzer of cobalt-plated inorganic and organic substances according to an embodiment of the present application; Figure 2 is a three-dimensional schematic diagram of the test chassis structure according to an embodiment of the present application; Figure 3 is a schematic diagram of the front view of the test chassis structure according to an embodiment of the present application; Figure 4 This is a system schematic diagram of an online analyzer for cobalt-plated inorganic and organic substances according to an embodiment of the present application; Figure 5 is a schematic diagram of the structure system of the colorimetric analysis unit and the titration analysis unit according to an embodiment of the present application; Figure 6 is a schematic diagram of a CVS analysis unit structure system according to an embodiment of the present application; Figure 7 It is a schematic diagram of the cobalt ion content analysis method according to an embodiment of the present application.

[0023] icon: 100, PLC control terminal; 200, sampling unit 1; 210, sampling pump 1; 220, defoaming channel 1; 230, tank liquid chamber 1; 300, sampling unit 2; 310, sampling pump 2; 320, defoaming channel 2; 330, tank liquid chamber 2; 400, multi-channel liquid supply valve group; 401, multi-channel valve 1; 402, multi-channel valve 2; 410, standard sample section; 420, pure water section 1; 430, sampling pump 3; 440, sampling pump 8; 500, colorimetric analysis unit; 510, sampling pump 4; 520, standard solution section; 530, solenoid valve 1; 540, clear Washing and draining section one; 600, titration analysis unit; 610, sampling pump seven; 620, titration standard liquid section; 630, solenoid valve two; 640, washing and draining section two; 650, sampling pump six; 660, auxiliary reagent section; 700, sampling pump five; 710, pure water section two; 800, CVS analysis unit; 810, sampling pump nine; 820, pure water section three; 830, sampling pump ten; 840, VMS storage section; 850, solenoid valve three; 860, washing and draining section three; 900, test chassis; 901, analysis chamber; 902, collection chamber; 903, sampling chamber. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be described below in conjunction with the drawings in the embodiments of the present application.

[0025] In order to make the purpose, technical solutions and advantages of the implementation methods of this application clearer, the technical solutions in the implementation methods of this application will be clearly and completely described below in conjunction with the drawings in the implementation methods of this application. Obviously, the described implementation methods are part of the implementation methods of this application, not all of the implementation methods. Based on the implementation methods in this application, all other implementation methods obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0026] Therefore, the following detailed description of the embodiments of the present application provided in the accompanying drawings is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present application.

[0027] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0028] In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise" and the like indicating orientations or positional relationships are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0029] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0030] In this application, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be directly connected or indirectly connected through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0031] In the present application, unless otherwise clearly specified and limited, a first feature being "above" or "below" a second feature may include that the first and second features are in direct contact, or may include that the first and second features are not in direct contact but are in contact through another feature between them. Moreover, a first feature being "above", "above" and "above" a second feature includes that the first feature is directly above and obliquely above the second feature, or simply indicates that the first feature is higher in level than the second feature. A first feature being "below", "below" and "below" a second feature includes that the first feature is directly below and obliquely below the second feature, or simply indicates that the first feature is lower in level than the second feature.

[0032] The following describes an online analyzer for cobalt-plated inorganic and organic substances according to an embodiment of the present application with reference to the accompanying drawings.

[0033] The key to this device is the design of an online analysis method for the concentration of boric acid, cobalt ions and trace organic additives in the cobalt plating bath. This technical solution uses acid-base neutralization titration to measure the concentration of boric acid, colorimetry to measure the concentration of cobalt ions, and electrochemical cyclic voltammetry stripping method CVS to measure the concentration of inhibitors. Automatic sampling of boric acid, cobalt ions and organic additives, and automatic analysis control are realized through the PLC program of the PLC control terminal 100, and the human-machine interface is designed in a touch screen manner.

[0034] Online analysis principle: Analysis parameters: boric acid concentration in the bath solution was 0-30 g / L, cobalt ion concentration was 0-3 g / L, and inhibitor concentration was 0-40 mL / L.

[0035] 1. Boric acid content analysis method: acid-base titration method Principle: Boric acid is a polybasic weak acid and cannot be directly titrated with alkali. Mannitol is added to form a hydroxyl complex with a dissociation degree much greater than that of boric acid. The boric acid-hydroxyl complex dissociates and releases H+, which can be directly titrated with alkali to determine the boric acid content in the bath.

[0036] The on-line analysis method of boric acid content is as follows: ① Reagents Mannitol solution: 10%~20% Sodium hydroxide solution NaOH: 0.1 mol / L ②End point determination: pH electrode ③Analysis steps Sampling: After the sample is filtered and pre-treated by defoaming, 1~5 mL of sample is extracted into the titration analysis unit 600 by using the sampling unit 1 200 and the sampling unit 2 300, and then diluted with DI water and mixed thoroughly.

[0037] Add auxiliary reagents: add a quantitative amount of mannitol solution to the above mixed solution and stir thoroughly until the mixture is uniform.

[0038] Titration: Use 0.1 mol / L NaOH standard solution for potentiometric titration, and use the change of pH electrode to determine the titration end point. The titration process curve can be displayed in real time. When the pH value has a sudden jump point, the titration end point is reached.

[0039] calculate: According to the chemical reaction relationship, the boric acid concentration in the sample is calculated using the consumption of NaOH solution. The formula is as follows: in: C NaOH is the concentration of NaOH solution in mol / L V NaOH is the volume of NaOH consumed L MH3BO3 The molar mass of boric acid is 61.83 g / mol V 样品 is the sample volume L Through this method, the content of boric acid in the cobalt plating solution can be accurately determined, which helps to control the composition stability of the plating solution and the quality of the coating.

[0040] 2. Cobalt ion content analysis method: single wavelength spectrophotometry Principle: Cobalt ions have specific absorption in the wavelength range of 510nm~530nm, and the absorption intensity and cobalt ion content conform to the Lambert-Beer law. Single-wavelength dual-path spectrophotometry is used to test cobalt ions. Figure 7 As shown in the figure: the composite light emitted from the light source is split by the monochromator and then passes through the reflector and the beam cutter. The beam cutter is used to alternately divide a beam of light into two beams of equal intensity at a certain frequency, so that one beam passes through the reference solution and the other passes through the sample solution. Then the detector periodically receives the reference signal and the sample signal alternately. After the received optical signal is converted into an electrical signal, the display system finally displays the result.

[0041] Since two beams of light pass through the reference solution and the sample solution at the same time, the error caused by the change in light source intensity can be automatically eliminated, thereby improving the sensitivity and accuracy of the measurement. In this way, the optical cutter can effectively reduce background noise, improve the signal-to-noise ratio of the instrument, and thus improve the reliability of the measurement results.

[0042] The online analysis method of cobalt ion content is as follows: 1. Reagents Prepare standard solutions according to the content of each component in the bath solution: when the content of other components remains unchanged, prepare a series of standard samples of known concentration using the cobalt ion content as a variable, and the cobalt ion content range is: ≤3.5g / L.

[0043] 2. Judgment: Colorimetric sensor 2 Analysis steps Preparation of standard samples: Use the test results of the standard solution to establish a standard curve and obtain the relationship equation. You can select 3 to 5 points within the above solution range as the curve for drawing, for example: 0g / L, 1g / L, 2g / L, 3g / L, 3.5g / L.

[0044] Sampling: After the standard solution is filtered and pre-treated with defoaming, 1~2 mL of sample is extracted into the colorimetric analysis unit 500 by using the sampling unit 1 200 or the sampling unit 2 300.

[0045] Standardization: Use a UV-visible spectrophotometer to measure the absorbance of each standard solution at a selected wavelength of 510 nm ~ 530 nm. According to the Lambert-Beer law, a standard curve of absorbance and concentration is drawn to obtain a linear equation.

[0046] Analysis: According to step 2, draw a sample of the bath solution into the colorimetric analysis unit 500, and measure the absorbance of the sample at the same selected wavelength of 510 nm.

[0047] Calculation: Calculate the actual concentration of cobalt ions in the bath sample in g / L based on the measured sample absorbance and the standard curve.

[0048] UV-Vis spectrophotometry can be used to quickly and accurately determine the cobalt ion content in the cobalt plating solution, which helps to monitor the composition of the plating solution and ensure the quality and consistency of the coating.

[0049] 3. Additive content analysis method: Cyclic Voltammetric Stripping, CVS Principle: Electrochemical CVS is a method commonly used to determine the content of organic additives in electroplating solutions. CVS is an electrochemical analysis method that uses a solution of the substance to be tested and a three-electrode system consisting of a working electrode WE, a reference electrode RE, and a counter electrode CE to form an electrolytic cell. It quantitatively analyzes additives by measuring the changes in voltage-current parameters during the electrolysis process.

[0050] Using the three-electrode system as the working unit, the cyclically changing voltage is set to positive and negative voltage values ​​to act on the closed loop formed by the working electrode and the counter electrode, and the positive and negative voltage limits are swept at a constant rate to change the potential on the working electrode / electrolyte interface, forcing the active substance on the working electrode to undergo oxidation / reduction reactions. The metal is deposited on the negative electrode part of the working electrode, and a reduction reaction occurs. When it returns to the positive electrode part, an oxidation reaction occurs, and this deposition will be stripped off, thereby obtaining the response current size when electrochemistry occurs on the electrode, recording the electrode potential and response current size in the process, and obtaining the corresponding current-voltage curve. The curve is integrated and calculated, and the inhibitor content can be indirectly measured by calculating the charge required to strip the metal deposits.

[0051] The specific analysis steps for inhibitors in the sample to be tested are as follows: 1 Reagents: Virgin Make-up Solution, VMS: A cobalt plating bath that does not contain any organic additives, usually containing cobalt salts, boric acid and sodium chloride, and the concentration must be consistent with the concentration of the main components of the bath sample.

[0052] Standard solutions with known additives: used for calibration and establishment of standard curves.

[0053] 2 End point determination: three-electrode system Working electrode: rotating 2mm platinum disk electrode, mainly used for research electrode; Reference electrode: calomel electrode, provides a stable reference potential to measure the potential / potential of the working electrode; Counter electrode: A platinum electrode that forms a circuit with the working electrode to provide a current path.

[0054] 3 Analysis steps Preparation of VMS: The solution contains 3 g / L cobalt ions, 30 g / L boric acid, and pH = 3.0; Determination of calibration factor: For the reference electrolyte, use an electrochemical workstation to measure and record the peak area Ar0. Add a known concentration of inhibitor standard solution to the reference electrolyte for no less than 3 times, with a concentration of C and a volume of V. Perform cyclic voltammetry scanning, record the peak area Ar, and calculate the Ar / Ar0 value as the end point.

[0055] Calculate the calibration factor: in: C end : The inhibitor concentration at the end is the calibration factor; C: standard inhibitor concentration; V: inhibitor addition volume; V VMS : Reference electrolyte volume.

[0056] Sample determination: Dilute the pretreated cobalt plating solution sample with DI water to an appropriate concentration range to ensure that Ar / Ar0 is less than the end value. Determine the Ar0 of the basic electrolyte, add the sample solution multiple times, draw a standard curve of Ar / Ar0-inhibitor addition, and calculate the linear regression equation.

[0057] Calculate the inhibitor concentration in the sample: in; C end : Calibration factor V: When C=C end When the inhibitor addition amount L V VMS :Basic electrolyte volume L By using cyclic voltammetry (CVS) with the calibration factor method, the inhibitor content in the cobalt plating solution can be accurately determined, which helps to optimize the plating solution formulation and ensure the quality and consistency of the plating layer.

[0058] like Figure 1-Figure 6It is shown that the cobalt-plated inorganic and organic online analyzer according to the embodiment of the present application includes a PLC control terminal 100 and a test chassis 900 for controlling the online analyzer, and the PLC control terminal 100 is bidirectionally electrically connected to the colorimetric analysis unit 500, the titration analysis unit 600, the CVS analysis unit 800, the sampling unit 1 200 and the sampling unit 2 300; the upper and lower ends of the inner cavity of the test chassis 900 are respectively provided with an analysis chamber 901 and a sampling chamber 903, wherein the inner cavity of the analysis chamber 901 is integrated with an analysis and test module, and the inner cavity of the sampling chamber 903 is integrated with a sampling module; the analysis chamber 901 is used to assemble the analysis and test module, and the sampling chamber 903 is used to assemble the sampling module; The middle section of the surface of the test box 900 is also provided with a collection chamber 902, which is used to place other auxiliary devices when testing the cobalt-plated inorganic and organic online analyzer; Meanwhile, the sampling module includes a sampling unit 1 200 and a sampling unit 2 300. The sampling unit 1 200 is used to perform sampling analysis on the colorimetric analysis unit 500 and the titration analysis unit 600, while the sampling unit 2 300 is used to perform liquid supply analysis on the CVS analysis unit 800. The sampling unit 200 includes a sampling pump 210, a defoaming channel 220 and a tank liquid chamber 230, wherein the tank liquid chamber 230 is used to store the tank liquid, and the output end of the tank liquid chamber 230 and the input end of the sampling pump 210 are connected by a pipeline. At the same time, the output end of the sampling pump 210 and the input end of the defoaming channel 220 are connected by a pipeline for defoaming the tank liquid, and the output end of the defoaming channel 220 and the input end of the tank liquid chamber 230 are connected to each other, so that the defoamed solution is sent to the tank liquid chamber 230 for storage.

[0059] The sampling unit 2 300 includes a sampling pump 2 310, a defoaming channel 2 320 and a tank liquid chamber 2 330, wherein the tank liquid chamber 2 330 is used to store the tank liquid, and the output end of the tank liquid chamber 2 330 and the input end of the sampling pump 2 310 are connected by a pipeline. At the same time, the output end of the sampling pump 2 310 and the input end of the defoaming channel 2 320 are connected by a pipeline for defoaming the tank liquid, and the output end of the defoaming channel 2 320 and the input end of the tank liquid chamber 2 330 are connected to each other, so that the defoamed solution is sent to the tank liquid chamber 2 330 for storage.

[0060] In this way, different defoamed reagent solutions are stored in the first tank liquid chamber 230 and the second tank liquid chamber 330 respectively.

[0061] The analysis and testing module and the sampling module are connected to increase liquid supply through a multi-channel liquid supply valve group 400, and the multi-channel liquid supply valve group 400 includes a multi-channel valve 1 401 and a multi-channel valve 2 402, wherein the output end of the multi-channel valve 1 401 is connected to a sampling pump 3 430, and the output end of the sampling pump 3 430 is interconnected with the input end of the colorimetric analysis unit 500 through a pipeline, so as to deliver the sampled solution into the colorimetric analysis unit 500 for testing, and the output end of the multi-channel valve 2 402 is connected to a sampling pump 8 440, and the output end of the sampling pump 8 440 is interconnected with the input end of the CVS analysis unit 800 through a pipeline, so as to deliver the sampled solution into the CVS analysis unit 800 for analysis and testing.

[0062] The multi-channel liquid supply valve group 400 also includes a standard sample section 410 and a pure water section 420, wherein the standard sample section 410 and the pure water section 420 are both two groups, the standard sample section 410 is used to store solution standards, and the pure water section 420 is used to store pure water. At the same time, the output ends of the first group of standard sample section 410 and the pure water section 420 are respectively connected to the input end of the multi-channel valve 401 through pipelines; the output ends of the second group of standard sample section 410 and the pure water section 420 are respectively connected to the output end of the multi-channel valve 402 through pipelines.

[0063] Thus, under the action of the multi-channel valve 401, the solutions in the sampling unit 1 200, the sampling unit 2 300, the standard sample part 410 and the pure water part 1 420 can be respectively sent into the multi-channel valve 1 401, and then sent into the colorimetric analysis unit 500 through the multi-channel valve 1 401 and the sampling pump 3 430; Under the action of multi-channel valve 2 402, the solutions in sampling unit 1 200, sampling unit 2 300, standard sample part 410 and pure water part 1 420 can be sent into multi-channel valve 2 402 through pipelines, and then sent into CVS analysis unit 800 through sampling pump 8 440 for analysis and testing.

[0064] The analysis and testing module includes a colorimetric analysis unit 500, a titration analysis unit 600 and a CVS analysis unit 800, which are used in combination to accurately analyze the tank liquid; the colorimetric analysis unit 500, the titration analysis unit 600 and the CVS analysis unit 800 are integrated and installed in the analysis chamber 901; Specifically, the inorganic test in the analytical test module includes colorimetric analysis calibration and titration analysis calibration; The input end of the colorimetric analysis unit 500 is connected to a sampling pump 24 510 through a pipeline, and the input end of the sampling pump 24 510 is connected to a standard solution unit 520 through a pipeline, and the output end of the standard solution unit 520 and the input end of the sampling pump 24 510 are connected to each other, so that the standard solution in the standard solution unit 520 can be pressurized and quickly sent into the colorimetric analysis unit 500 through the sampling pump 24 510. The colorimetric analysis unit 500 is connected to the cleaning and waste discharge part 540 through a pipeline, and in order to open and close the pipeline between the colorimetric analysis unit 500 and the cleaning and waste discharge part 540, a solenoid valve 530 is installed on the pipeline between the cleaning and waste discharge part 540 and the colorimetric analysis unit 500; The input end of the titration analysis unit 600 is connected to a sampling pump 610 through a pipeline, and the input end of the sampling pump 610 is connected to a titration standard liquid unit 620 through a pipeline, and the output end of the titration standard liquid unit 620 and the input end of the sampling pump 610 are connected to each other, so that the standard liquid in the titration standard liquid unit 620 can be pressurized and quickly sent into the titration analysis unit 600 through the sampling pump 610. The titration analysis unit 600 is connected to the second cleaning and draining part 640 through a pipeline, and in order to open and close the pipeline between the titration analysis unit 600 and the second cleaning and draining part 640, a second solenoid valve 630 is installed on the pipeline between the second cleaning and draining part 640 and the titration analysis unit 600; The input end of the titration analysis unit 600 is also connected to a sampling pump 650 through a pipeline, wherein the input end of the sampling pump 650 and the output end of the auxiliary reagent unit 660 are connected to each other through a pipeline.

[0065] The colorimetric analysis unit 500 and the titration analysis unit 600 are both connected to a sampling pump 5 700 via a pipeline, and the input end of the sampling pump 5 700 is connected to the pure water part 2 710, and the output end of the sampling pump 5 700 is respectively connected to the colorimetric analysis unit 500 and the titration analysis unit 600 via pipelines, so that the pure water in the pure water part 2 710 is delivered to the colorimetric analysis unit 500 and the titration analysis unit 600 through the sampling pump 5 700.

[0066] The sampling pump 1 210 is a tank liquid sampling peristaltic pump, which extracts the tank liquid in the tank liquid chamber 1 230 to the sampling unit 1 200; The second sampling pump 310 is a tank liquid sampling peristaltic pump, which extracts the tank liquid in the second tank liquid chamber 330 to the second sampling unit 300; The sampling pump 3 430 is an analytical sampling pump, specifically a peristaltic pump or a diaphragm pump, which extracts the tank liquid / standard sample to the colorimetric analysis unit 500; Multi-channel valve 401 has 3 inputs and 1 output: the standard sample part 410 and the pure water part 420 are switched for sampling The colorimetric analysis unit 500 includes a colorimetric sensor for online analysis of the content of cobalt ions in the bath solution; The sampling pump 4 510 is a pulse peristaltic pump, which extracts the calibration standard solution of the standard solution part 520 to the colorimetric analysis unit 500; The sampling pump 5 700 is a diaphragm pump, which draws pure water to the colorimetric analysis unit 500 and the titration analysis unit 600 for calibration and cleaning; Solenoid valve 1 530 is used to control the discharge of waste liquid from the colorimetric analysis unit 500 after the colorimetric analysis is completed; The sampling pump 650 is a pulse peristaltic pump, which is used to extract the auxiliary reagent mannitol for boric acid titration analysis in the auxiliary reagent part 660; The sampling pump 7 610 is a pulse peristaltic pump, which extracts the titration standard solution in the titration standard solution part 620 to the titration analysis unit 600; Solenoid valve 2 630 is used to discharge waste liquid after the titration reaction is completed. The titration analysis unit 600 comprises a pH composite electrode, a reaction cup and supporting components, and a stirring device, and is used for titration analysis of boric acid.

[0067] Cobalt plating online analysis of inorganic testing work steps: 1. Calibration part 1. Colorimetric Calibration Before analysis, the colorimetric sensor needs to be calibrated online. The specific calibration steps are as follows: ① Check whether each pump is used abnormally and test it after removing the bubbles in the pipeline; ② Turn on the sampling pump 5700 to extract pure water for flushing. The flushing time and number of times can be set and turned on at the same time; ③ Turn on the sampling pump 4510, extract the colorimetric calibration standard solution 1, which can be pure water or a solution with a known cobalt ion content, for rinsing, and the rinsing time can be set; ④ Test the absorbance of colorimetric calibration standard solution 1; ⑤ Turn on the sampling pump 5700 to extract pure water to clean the colorimetric sensor in the colorimetric analysis unit 500. The cleaning time and number of times can be set; ⑥Manually replace the standard solution and repeat steps ②, ③ and ④; ⑦ Choose any 3 to 5 standard solutions to establish a standard curve and obtain a linear equation. The calibration is now complete.

[0068] 2 Titration Calibration Before titration analysis, the pH electrode needs to be calibrated online using a 2-point calibration. The specific calibration steps are as follows: ① Check whether each pump is used abnormally and whether the pipeline is leaking; ② Open the sampling pump 5700 to extract pure water to rinse the electrodes in the reaction cup. After the set flushing time is reached, open the solenoid valve 2630 to discharge the waste liquid; ③ Extract pH standard solution 1 to the colorimetric analysis unit 500 to rinse the pH electrode; ④ Determine whether the signal V1 of the pH standard sample 1 is correct. If so, the PLC control terminal 100 automatically records the signal value of the pH standard sample 1. Otherwise, the alarm program is started to give an alarm message; ⑤Repeat steps ②, ③ and ④; According to the signal values ​​recorded twice, calculate the slope and intercept of the linear equation: pH=kx+B. If both are within the specified range, the calibration is completed; otherwise, repeat the above calibration steps.

[0069] 2. Test part ① Turn on the sampling pump 210, extract the tank liquid in the tank liquid chamber 230, rinse and reflux in the pipeline; ② Open the sampling pump 3 430 and the corresponding valve ports of the multi-channel valve 1 401 to quantitatively extract the tank liquid in the tank liquid chamber 1 230 to the colorimetric analysis unit 500; ③ In the colorimetric analysis unit 500, the real-time absorbance is measured when the cobalt ion concentration in the bath solution passes through the colorimetric sensor. The concentration value is calculated by the system using the calibration curve, automatically recorded and saved, and the test of the colorimetric analysis unit 500 is completed; ④ The tank liquid flows through the colorimetric analysis unit 500 and reaches the titration analysis unit 600; ⑤ The titration analysis unit 600 first starts the pump to extract an appropriate amount of auxiliary reagent to obtain a boric acid complex to achieve the effect of weak acid strengthening. At this time, the volume of the solution in the reaction cup is recorded as V0; ⑥ Start stirring and titrate with standard titration solution to the titration endpoint to complete the boric acid analysis. Record the titration volume as V1 and calculate the boric acid content by the following formula.

[0070] ⑦ After the calculation is completed, open the solenoid valve 2630 to discharge the waste water, and the measured boric acid concentration value is recorded and output; ⑧After the analysis is completed, the sampling pump 210 is reversed to empty the tank liquid in the pipeline and extract pure water to clean the sampling pipeline. The cleaning frequency and time can be set; ⑨ While cleaning the sampling pipeline, turn on the sampling pump 5700 to extract pure water for spraying and flushing. The flushing time and number of times can be set; ⑩Open the solenoid valve 2630 to discharge waste; ⑪ Repeat the above steps ① to ⑩ to test the bath liquid in the bath liquid chamber 2 330.

[0071] Specifically, the organic test in the analysis and testing module includes CVS analysis test; The CVS analysis unit 800 is connected to the pure water unit 3 820 and the VMS storage unit 840 through pipelines, wherein the output end of the pure water unit 3 820 is connected to the sampling pump 9 810 through a pipeline, and the output end of the sampling pump 9 810 and the input end of the CVS analysis unit 800 are connected to each other through a pipeline, and the output end of the VMS storage unit 840 is connected to the sampling pump 10 830 through a pipeline, and the output end of the sampling pump 10 830 and the input end of the CVS analysis unit 800 are connected to each other; In this way, the pure water in the pure water section three 820 can be sent to the CVS analysis unit 800 through the sampling pump nine 810, and the solution in the VMS storage section 840 can be sent to the CVS analysis unit 800 through the pure water section three 820 for analysis and testing.

[0072] The CVS analysis unit 800 is connected to the cleaning and waste discharge part 3 860 through a pipeline, and a solenoid valve 3 850 is installed on the pipeline on the surface of the cleaning and waste discharge part 3 860. The solenoid valve 3 850 is used to control the on-off of the pipeline on the cleaning and waste discharge part 3 860.

[0073] The sampling pump eight 440 is equipped with a multi-channel valve two 402 for switching the injection of the standard sample part 410 and the pure water part one 420; The sampling pump 8440 is a high-precision syringe pump used to extract the tank liquid to the CVS analysis unit 800; The sampling pump nine 810 is a diaphragm pump, which extracts pure water in the pure water section three 820 to the CVS analysis unit 800 for calibration and cleaning; The sampling pump 830 is a high-precision syringe pump, which extracts the base liquid VMS used to dilute the sample in the VMS storage unit 840; Solenoid valve 3 850 can be opened to discharge waste liquid after the CVS analysis unit 800 test is completed; The CVS analysis unit 800 includes a three-electrode test system and a reaction cup and its supporting components.

[0074] Cobalt plating online analysis organic test work steps: CVS analysis preparation Before titration analysis, it is necessary to check the status of each electrode in the CVS three-electrode system and calibrate the syringe pump. The specific steps are as follows: I Electrode status check: ① Working electrode: Ensure that the electrode surface is smooth and avoid scratches or mechanical operations on the surface; ② Reference electrode: The internal reference and external reference of the reference solution need to be replenished regularly to ensure that there are no bubbles; ③ Counter electrode: Ensure that the electrode surface is smooth, flat and free of adhesion.

[0075] II Syringe Pump Calibration: ①Use the online analysis software system, select the syringe pump number in the calibration interface, prepare the electronic balance and beaker, and peel the beaker in advance; ② Click the start button to reset the injection pump, which will automatically stop after resetting; ③ Set the number of pulses, click Start, switch to the water inlet valve, let the syringe pump extract a fixed volume of pure water, and then exhaust to ensure that there are no bubbles in the liquid; ④ When the syringe pump operation status prompts the next action, use a beaker to collect the pure water discharged by the syringe pump at the water outlet. When the volume of water collected in the beaker is about 10mL, click Stop; ⑤ Use an electronic balance to obtain the weight of pure water, corresponding to the volumetric density of pure water, which is 1g / cm3; ⑥ Repeat steps ②~⑤ and measure the average value 10 times in parallel; Enter the average value into the correction part volume box. The current number of pulses corresponds to the volume at this time, and the calibration is completed.

[0076] Organic Testing Steps: ① Open the sampling pump 830 to extract the base liquid VMS from the VMS storage unit 840 to rinse the pipeline, and discharge the waste liquid after completion; ②Calculate the calibration factor for additive calibration: The sampling pump 830 extracts quantitative VMS to the CVS analysis unit 800, and the three-electrode system performs cyclic voltammetry scanning, and the VMS peak area Ar0 is recorded. The sampling pump 8440 extracts quantitative tank liquid standard samples multiple times, with a concentration of C and a volume of V, and the peak area Ar is recorded. The Ar / Ar0 is measured after each addition, and the end value is set to <1 and stops. Calculate the calibration factor: ③Analyze the tank solution: After the sampling pump + 830 extracts VMS to measure Ar0, add a quantitative unknown concentration tank solution multiple times. Measure Ar / Ar0 after each addition, and stop adding tank solution when the end value is reached. Calculate the unknown tank solution concentration: The same VMS, the same Ar0, the same inhibitor, the same Ar effect. Therefore, the calibration factor Cend obtained by the standard solution can be used to detect the unknown concentration of the inhibitor in the bath solution, and the measured additive concentration value is recorded and output; ④ After the calculation is completed, open the solenoid valve 3850 to discharge the waste liquid.

[0077] Specifically, the online analysis instrument for inorganic and organic matter in cobalt plating prompts If the following situations occur during the test, the system will sound an alarm and display an alarm message.

[0078] ① When the sampling pump 1 210 and the sampling pump 2 310 perform the sampling step, no tank liquid is pumped, and a flow interruption alarm is prompted; ② During the analysis process of colorimetry, titration, and CVS, if the analysis time exceeds the set value, a timeout alarm will be prompted; ③ If the test value exceeds the set upper limit or is lower than the lower limit, an over-limit alarm will be prompted: ④ For reagents, standard solutions, pure water, etc. used in the analysis, if the liquid level in the storage container is lower than the set value, a low liquid level alarm will be prompted; ⑤ When the liquid level in the waste liquid storage container is higher than the set value, a high liquid level alarm is prompted; ⑥ The analytical instrument has a self-checking function. If it is not executed according to the setting, an alarm will be prompted; ⑦ After the calibration is due, if online / manual calibration is not performed in time, an alarm will be prompted; ⑧When the key components used reach their service life, a maintenance alarm will be prompted.

[0079] Specifically, the functions of the on-line analyzer for inorganic and organic matter in cobalt plating are: ① This device can be connected to the automatic dosing unit, and the dosing unit can be controlled to automatically add a solution containing boric acid, cobalt ions and additives according to the analysis results; ② This device can automatically adjust the addition amount according to the results of multiple consecutive analyses, making the process parameters more stable; ③ The device uses Ethernet TCP / IP network communication, and can upload analysis, dosing, and alarm information to the customer's MES system according to the Modbus protocol; ④ The analysis system of this device is automatically cleaned; ⑤ Fixed-point analysis of the device and external trigger analysis; ⑥This device has multiple fool-proof alarm functions; ⑦ The analysis, dosing and alarm information of this device can be stored and exported.

[0080] The above are only embodiments of the present application and are not intended to limit the scope of protection of the present application. For those skilled in the art, the present application may have various changes and variations. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application. It should be noted that similar reference numerals and letters represent similar items in the following drawings, so once an item is defined in one drawing, it does not need to be further defined and explained in the subsequent drawings.

[0081] The above are only specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present application, which should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. An on-line analyzer for cobalt-plated inorganic and organic substances, characterized in that: include: A PLC control terminal (100), and a test box (900) for controlling an online analytical instrument, wherein an analysis chamber (901) and a sampling chamber (903) are respectively provided at the upper and lower ends of an inner cavity of the test box (900), wherein an analysis test module is integrated into the inner cavity of the analysis chamber (901), and a sampling module is integrated into the inner cavity of the sampling chamber (903); The analysis and testing module includes a colorimetric analysis unit (500), a titration analysis unit (600) and a CVS analysis unit (800), which are used in combination to accurately analyze the tank liquid; At the same time, the sampling module includes a sampling unit 1 (200) and a sampling unit 2 (300), wherein the sampling unit 1 (200) is used to perform sampling analysis on the colorimetric analysis unit (500) and the titration analysis unit (600), while the sampling unit 2 (300) is used to perform liquid supply analysis on the CVS analysis unit (800).

2. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 1, characterized in that: The sampling unit 1 (200) comprises a sampling pump 1 (210), a defoaming channel 1 (220) and a tank liquid chamber 1 (230), wherein: The tank liquid chamber 1 (230) is used to store the tank liquid, and the output end of the tank liquid chamber 1 (230) and the input end of the sampling pump 1 (210) are connected through a pipeline. At the same time, the output end of the sampling pump 1 (210) and the input end of the defoaming channel 1 (220) are connected through a pipeline, and the output end of the defoaming channel 1 (220) and the input end of the tank liquid chamber 1 (230) are connected to each other.

3. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 2, characterized in that: The sampling unit 2 (300) includes a sampling pump 2 (310), a defoaming channel 2 (320) and a tank liquid chamber 2 (330), wherein the tank liquid chamber 2 (330) is used to store the tank liquid, and the output end of the tank liquid chamber 2 (330) and the input end of the sampling pump 2 (310) are connected through a pipeline. At the same time, the output end of the sampling pump 2 (310) and the input end of the defoaming channel 2 (320) are connected through a pipeline, and the output end of the defoaming channel 2 (320) and the input end of the tank liquid chamber 2 (330) are connected to each other.

4. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 3, characterized in that: Liquid is added between the analysis and testing module and the sampling module via a multi-channel liquid supply valve group (400), and the multi-channel liquid supply valve group (400) includes a multi-channel valve one (401) and a multi-channel valve two (402), wherein the output end of the multi-channel valve one (401) is connected to a sampling pump three (430), and the output end of the multi-channel valve two (402) is connected to a sampling pump eight (440).

5. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 4, characterized in that: The multi-channel liquid supply valve group (400) further comprises a standard sample section (410) and a pure water section one (420), wherein the standard sample section (410) and the pure water section one (420) are each two groups, the standard sample section (410) is used to store solution standards, and the pure water section one (420) is used to store pure water.

6. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 5, characterized in that: The input end of the colorimetric analysis unit (500) is connected to a sampling pump four (510) through a pipeline, and the input end of the sampling pump four (510) is connected to a standard solution unit (520) through a pipeline; The colorimetric analysis unit (500) is connected to a cleaning waste discharge part (540) via a pipeline, and a solenoid valve (530) is installed on the pipeline between the cleaning waste discharge part (540) and the colorimetric analysis unit (500).

7. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 6, characterized in that: The input end of the titration analysis unit (600) is connected to a sampling pump (610) via a pipeline, and the input end of the sampling pump (610) is connected to a titration standard liquid unit (620) via a pipeline; The titration analysis unit (600) is connected to a second cleaning and drainage unit (640) via a pipeline, and a second solenoid valve (630) is installed on the pipeline between the second cleaning and drainage unit (640) and the titration analysis unit (600); The input end of the titration analysis unit (600) is also connected to a sampling pump six (650) through a pipeline, wherein the input end of the sampling pump six (650) and the output end of the auxiliary reagent unit (660) are connected to each other through a pipeline.

8. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 7, characterized in that: The colorimetric analysis unit (500) and the titration analysis unit (600) are both connected to a sampling pump five (700) via pipelines, and the input end of the sampling pump five (700) is connected to the pure water unit two (710), while the output end of the sampling pump five (700) is connected to the colorimetric analysis unit (500) and the titration analysis unit (600) via pipelines.

9. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 8, characterized in that: The CVS analysis unit (800) is connected to the pure water section three (820) and the VMS storage section (840) through pipelines, wherein the output end of the pure water section three (820) is connected to the sampling pump nine (810) through a pipeline, and the output end of the VMS storage section (840) is connected to the sampling pump ten (830) through a pipeline.

10. The on-line analyzer for cobalt-plated inorganic and organic substances according to claim 9, characterized in that: The CVS analysis unit (800) is connected to the cleaning and waste discharge part three (860) through a pipeline, and a solenoid valve three (850) is installed on the pipeline on the surface of the cleaning and waste discharge part three (860), and the solenoid valve three (850) is used to control the on-off of the pipeline on the cleaning and waste discharge part three (860).

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