CN119470311A - An online analysis instrument for cobalt-plated inorganic and organic substances - Google Patents

Abstract

The embodiment of the present application provides an online analyzer for inorganic and organic cobalt plating, which relates to the field of cobalt plating detection. The online analyzer for inorganic and organic cobalt plating includes a PLC control terminal and a test chassis, 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 testing 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 in combination to accurately analyze the tank liquid; at the same time, the sampling module includes sampling unit one and sampling unit two. The present device proposes an online analyzer for inorganic and organic cobalt plating, which can accurately measure the concentration of boric acid, cobalt ions and inhibitor additives in the plating solution to optimize the metallization process in semiconductor manufacturing.

Description

Online analysis instrument for cobalt-plated inorganic matters and organic matters

Technical Field

The application relates to the technical field of cobalt plating detection, in particular to an online analysis instrument for cobalt plating inorganic matters and organic matters.

Background

In the semiconductor industry, the fabrication process of silicon chips involves a multi-step precision process. Among these, metallization processes are a critical ring, typically by depositing metal layers on silicon wafers to form electrodes and wires. In this process, cobalt plating technology is widely used in copper interconnect interlayers to enhance electromigration resistance and reduce electrical resistance. Meanwhile, additives such as boric acid and cobalt ions play an important role in the cobalt plating process, and can adjust the properties of the electroplating solution and improve the uniformity and performance of the plating layer. Therefore, developing a highly efficient cobalt plating analyzer to accurately determine the concentrations of boric acid, cobalt ions, and inhibitor additives is of great importance in optimizing the cobalt plating process and improving the performance of semiconductor devices.

Boric acid acts as a buffer during electroplating and is primarily used to maintain the pH of the electroplating solution stable. The method can effectively prevent the acidification of the electroplating solution caused by the generation of hydrogen ions in the electrolytic reaction, thereby ensuring the smooth progress of the electroplating process. In addition, the boric acid can also increase the conductivity of the electroplating solution and improve the electroplating efficiency and the plating quality. Boric acid helps form a dense, uniform and nonporous coating by maintaining a suitable pH environment.

Cobalt ions are the main component in forming a cobalt plating layer during electroplating. It is reduced in electrolytic reaction and deposited on the surface of the base material to form compact metal cobalt coating. Cobalt plating has excellent hardness, wear resistance and corrosion resistance, and is therefore widely used in many demanding applications. The concentration of cobalt ions has a direct effect on the structure and performance of the coating, and optimizing the concentration of cobalt ions helps to achieve the desired coating characteristics.

The inhibitor additive plays a key role in regulating and controlling in the electroplating process. They inhibit the reduction of metal ions in localized areas by adsorption on the substrate surface, thereby controlling the growth rate and uniformity of the coating. These additives can prevent dendrite formation, reduce voids and defects in the coating, and promote the smoothness and consistency of the coating. Different kinds of inhibitor additives can adjust the physical and chemical properties of the coating as required to meet the requirements of a particular application.

Therefore, the development of the high-efficiency cobalt plating analyzer can accurately measure the concentrations of boric acid, cobalt ions and inhibitor additives, and has important significance for optimizing the cobalt plating process and improving the performance of semiconductor devices. The technical background and innovation of this patent is based on these critical requirements, aiming at providing an effective solution to ensure precise control of the components during the electroplating process and to ensure high quality of the final product.

Disclosure of Invention

The present application aims to solve at least one of the technical problems existing in the prior art. Therefore, the application provides an on-line analysis instrument for cobalt-plated inorganic matters and organic matters, which aims to accurately measure the concentrations of boric acid, cobalt ions and inhibitor additives in electroplating liquid so as to optimize the metallization process in semiconductor manufacturing. The analyzer can ensure stable pH and good conductivity in the electroplating process, and effectively control the uniformity and performance of the plating layer, thereby improving the hardness, wear resistance and corrosion resistance of the cobalt plating layer, reducing defects and pores, and finally improving the overall performance and reliability of the semiconductor device.

The cobalt-plated inorganic and organic matter online analysis instrument comprises a PLC control terminal and a testing machine box for controlling the online analysis instrument, wherein an analysis chamber and a sampling chamber are respectively arranged at the upper end and the lower end of an inner cavity of the testing machine box, an analysis testing module is integrally arranged in the inner cavity of the analysis chamber, and a sampling module is integrally arranged in the inner cavity of the sampling chamber;

The analysis and test module comprises a colorimetric analysis unit, a titration analysis unit and a CVS analysis unit which are matched for use and are used for accurately analyzing the groove liquid;

Meanwhile, the sampling module comprises a first sampling unit and a second sampling unit, wherein the first sampling unit is used for sampling and analyzing the colorimetric analysis unit and the titration analysis unit, and the second sampling unit is used for carrying out liquid supply analysis on the CVS analysis unit.

According to some embodiments of the application, the first sampling unit includes a first sampling pump, a first defoaming channel, and a first tank chamber, wherein the first tank chamber is used for storing tank liquid, and an output end of the first tank chamber is connected to an input end of the first sampling pump through a pipeline, and at the same time, an output end of the first sampling pump is connected to an input end of the first defoaming channel through a pipeline, and an output end of the first defoaming channel is connected to an input end of the first tank chamber.

According to some embodiments of the application, the second sampling unit includes a second sampling pump, a second defoaming channel, and a second tank chamber, where the second tank chamber is used for storing tank liquid, and an output end of the second tank chamber is connected to an input end of the second sampling pump through a pipeline, and at the same time, an output end of the second sampling pump is connected to an input end of the second defoaming channel through a pipeline, and an output end of the second defoaming channel is connected to an input end of the second tank chamber.

According to some embodiments of the application, the liquid feeding is increased between the analysis and test module and the sampling module through a multi-channel liquid feeding valve group, wherein the multi-channel liquid feeding valve group comprises a multi-channel valve I and a multi-channel valve II, the output end of the multi-channel valve I is communicated with a sampling pump III, and the output end of the multi-channel valve II is communicated with a sampling pump eight.

According to some embodiments of the application, the multi-channel valve block further comprises a standard sample part and a pure water part, wherein the standard sample part and the pure water part are two groups, the standard sample part is used for storing the solution standard sample, and the pure water part is used for storing the pure water.

According to some embodiments of the application, the input end of the colorimetric analysis unit is communicated with a sampling pump IV through a pipeline, and the input end of the sampling pump IV is communicated with a standard solution part through a pipeline;

the colorimetric analysis unit is communicated with a first cleaning waste discharge part through a pipeline, and a first electromagnetic valve is installed on the pipeline between the first cleaning waste discharge part and the colorimetric analysis unit.

According to some embodiments of the application, the input end of the titration analysis unit is communicated with a sampling pump seven through a pipeline, and the input end of the sampling pump seven is communicated with a titration standard liquid part through a pipeline;

the titration analysis unit is communicated with a second cleaning liquid draining part through a pipeline, and a second electromagnetic valve is arranged on the pipeline between the second cleaning liquid draining part and the titration analysis unit;

the input end of the titration analysis unit is also communicated with a sampling pump six through a pipeline, wherein the input end of the sampling pump six is communicated with the output end of the auxiliary reagent part through a pipeline.

According to some embodiments of the present application, the colorimetric analysis unit and the titration analysis unit are both communicated with the sampling pump five through a pipeline, the input end of the sampling pump five is communicated with the pure water part II, and the output end of the sampling pump five is respectively communicated with the colorimetric analysis unit and the titration analysis unit through pipelines.

According to some embodiments of the application, the CVS analysis unit is respectively connected to a third pure water part and a VMS storage part through pipelines, wherein an output end of the third pure water part is connected to a sampling pump nine through a pipeline, and an output end of the VMS storage part is connected to a sampling pump ten through a pipeline.

According to some embodiments of the application, the CVS analysis unit is communicated with a third cleaning and waste discharging part through a pipeline, a third electromagnetic valve is installed on the pipeline on the surface of the third cleaning and waste discharging part, and the third electromagnetic valve is used for controlling the on-off of the pipeline on the third cleaning and waste discharging part.

The device has the advantages that the concentration of boric acid, cobalt ions and inhibitor additives in the electroplating liquid is accurately measured, the stability and consistency of the quality of a coating are ensured, the production efficiency is greatly improved through the capability of real-time monitoring and analysis, complicated sample preparation and long-time detection processes are reduced, dependence on professionals is reduced through automatic operation, the operation difficulty and error risk are reduced, the real-time monitoring function ensures that the process problem can be rapidly found and corrected, the production cost is obviously reduced, the high sensitivity of the device can detect the tiny change of low-concentration components, and the uniformity and performance of the coating are ensured.

These advantages make the cobalt-plated inorganic and organic on-line analytical instrument an ideal choice for optimizing the electroplating process and improving the product quality. The online analysis instrument for the cobalt-plated inorganic matters and the organic matters can complete the measurement in real time and high efficiently, and remarkably improves the production efficiency and the process control precision.

Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and should not be considered as limiting the scope, and other related drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a schematic perspective view of the overall structure of an on-line analysis instrument for cobalt-plated inorganic and organic matters according to an embodiment of the present application;

FIG. 2 is a schematic perspective view of a test case according to an embodiment of the present application;

FIG. 3 is a schematic diagram of a front view of a test chassis structure according to an embodiment of the present application;

FIG. 4 is a system schematic diagram of an on-line cobalt-plated inorganic and organic matter analysis instrument according to an embodiment of the application;

FIG. 5 is a schematic diagram of the structural system of a colorimetric and titration analysis unit in accordance with an embodiment of the present application;

FIG. 6 is a schematic diagram of a CVS analysis Unit architecture system according to an embodiment of the present application;

fig. 7 is a schematic diagram of a cobalt ion content analysis method according to an embodiment of the present application.

Icon:

100. A PLC control terminal; 200, first sampling unit, 210, first sampling pump, 220, first defoaming channel, 230, first tank chamber, 300, second sampling unit, 310, second sampling pump, 320, second defoaming channel, 330, second tank chamber, 400, multi-channel liquid supply valve set, 401, first multi-channel valve, 402, second multi-channel valve, 410, standard sample part, 420, first pure water part, 430, third sampling pump, 440, eighth sampling pump, 500, colorimetric analysis unit, 510, fourth sampling pump, 520, standard solution part, 530, first solenoid valve, 540, first cleaning waste discharge part, 600, titration analysis unit, 610, seventh sampling pump, 620, titration standard liquid part, 630, second solenoid valve, 640, cleaning waste liquid part, 650, sixth sampling pump, 660, auxiliary reagent part, 700, fifth sampling pump, 710, second pure water part, 800, CVS analysis unit, 810, ninth sampling pump, 820, third pure water part, 830, tenth sampling pump, 840, third storage part, 850, third solenoid valve, 860, third cleaning waste discharge part, 901, third testing machine case, 903, sampling chamber, VMS analysis chamber, and collecting chamber.

Detailed Description

The technical solutions in the embodiments of the present application will be described below with reference to the accompanying drawings in the embodiments of the present application.

For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application.

Thus, the following detailed description of the embodiments of the application, as presented in the figures, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application.

It should be noted that like reference numerals and letters refer to like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.

In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present application and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present application.

Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.

In the present application, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed, directly connected, indirectly connected via an intermediate medium, or in communication with each other between two elements or in an interaction relationship between two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.

In the present application, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.

An apparatus for on-line analysis of cobalt-plated inorganic and organic matters according to an embodiment of the present application is described below with reference to the accompanying drawings.

The key point of the device is the design of an online analysis method for the concentration of boric acid, cobalt ions and trace organic additives in cobalt plating bath solution. Automatic sampling of boric acid, cobalt ions and organic additives, automatic analysis control is realized through a PLC program of the PLC control terminal 100, and a human-computer interface is designed in a touch screen mode.

On-line analysis principle:

the analysis parameters are that the concentration of boric acid in the tank liquor is 0-30 g/L, the concentration of cobalt ions is 0-3 g/L and the concentration of inhibitors is 0-40 mL/L.

1. Boric acid content analysis method, acid-base titration method

The principle is that boric acid belongs to a polybasic weak acid, and can not be directly titrated by alkali, mannitol is added, and the boric acid is combined to generate a hydroxyl complex with dissociation degree far greater than that of boric acid. The boric acid-hydroxyl complex is dissociated to separate out H+, and the H+ can be directly titrated by alkali to measure the boric acid content in the tank liquor.

The boric acid content on-line analysis method specifically comprises the following steps:

① Reagent(s)

10-20% Of mannitol solution

NaOH solution 0.1 mol/L

② Endpoint determination pH electrode

③ Analytical procedure

Sampling, namely filtering and defoaming the sample, extracting 1-5 mL of the sample to the titration analysis unit 600 by means of the first sampling unit 200 and the second sampling unit 300, diluting with DI water, and fully and uniformly mixing.

Adding auxiliary reagent, adding quantitative mannitol solution into the above mixed solution, and stirring thoroughly until mixing well.

Titration, namely potentiometric titration is carried out by using 0.1 mol/L NaOH standard solution, the titration end point is judged by utilizing the change of a pH electrode, and a titration process curve can be displayed in real time, and when the pH value has a jump point, the titration end point is reached.

And (3) calculating:

According to the chemical reaction relation, the consumption of NaOH solution is utilized to calculate the boric acid concentration in the sample, and the formula is as follows:

Wherein:

C _NaOH is the concentration mol/L of NaOH solution

V _NaOH is the volume L consumed by NaOH

M _H3BO3 is the molar mass 61.83 g/mol of boric acid

V _{Sample of} is the sample volume L

By the method, the content of boric acid in the cobalt plating solution can be accurately measured, and the stability of components of the plating solution and the quality of the plating layer can be controlled.

2. Cobalt ion content analysis method by single wavelength spectrophotometry

The principle is that cobalt ions have specific absorption in the wavelength range of 510 nm-530 nm, and the absorption strength and the cobalt ion content accord with the lambert-beer law. And testing cobalt ions by adopting a single-wavelength double-light-path spectrophotometry. The single wavelength dual light path spectrophotometry is shown in figure 7, wherein the single color light of the composite light emitted from the light source after being split by the monochromator passes through the reflector and the light chopper, and the light chopper is used for alternately dividing one light beam into two light beams with equal intensity at a certain frequency, so that one light beam passes through the reference solution, and the other light beam passes through the sample solution. The reference signal and the sample signal are then periodically and alternately received by the detector. And finally, the display system displays the result after the received optical signal is converted into an electric signal.

Because the two beams of light simultaneously pass through the reference solution and the sample solution, errors caused by the intensity change of the light source can be automatically eliminated, and the sensitivity and the accuracy of measurement are improved. By the mode, the light chopper can effectively reduce background noise, improve the signal-to-noise ratio of the instrument and further improve the reliability of a measuring result.

The cobalt ion content on-line analysis method specifically comprises the following steps:

1 reagent

Preparing standard solution according to the content of each component in the bath solution, namely preparing standard samples with known concentration by taking cobalt ion content as a variable under the condition that the content of the rest components is unchanged, wherein the content range of the cobalt ion is less than or equal to 3.5g/L.

2-Determination colorimetric sensor

2 Analysis step

Standard sample preparation, namely establishing a standard curve according to the test result of the standard solution to obtain a relation equation, wherein 3-5 points can be arbitrarily selected as curves in the range of the solution to draw, for example, 0g/L, 1g/L, 2g/L, 3g/L and 3.5g/L.

Sampling, namely filtering and defoaming the standard solution, and then extracting 1-2 mL of sample to the colorimetric analysis unit 500 by means of the first sampling unit 200 or the second sampling unit 300.

And (3) marking, namely measuring the absorbance of each standard solution at the selected wavelength of 510-530 nm by using an ultraviolet-visible spectrophotometer, and drawing a standard curve of absorbance and concentration according to the lambert-beer law to obtain a linear equation.

Analysis, the sample of the bath solution is extracted to a colorimetric analysis unit 500 according to the step 2, and the absorbance of the sample is measured at the same selected wavelength 510 nm.

Calculating the actual concentration g/L of cobalt ions in the bath solution sample according to the measured absorbance of the sample and the standard curve.

The content of cobalt ions in the cobalt plating solution can be rapidly and accurately measured by an ultraviolet-visible spectrophotometry, which is helpful for monitoring the components of the plating solution and ensuring the quality and consistency of the plating layer.

3. Additive content analysis method, cyclic voltammetry stripping Cyclic Voltammetric Stripping, CVS

Electrochemical CVS is a method commonly used to determine the content of organic additives in electroplating baths. CVS is an electrochemical analysis method for quantitatively analyzing additives by measuring the change of voltage-current parameters in the electrolysis process by forming an electrolytic cell by a substance solution to be detected, a working electrode WE, a reference electrode RE and a counter electrode CE of a three-electrode system.

The three-electrode system is used as a working unit, a cyclically-changed voltage is set to a positive voltage value and a negative voltage value to act on a closed loop formed by a working electrode and a counter electrode, the limit of positive and negative voltages is swept at a constant speed, the potential on the interface of the working electrode and an electrolyte is changed, the active substance on the working electrode is forced to undergo oxidation/reduction reaction, metal is deposited on the negative electrode part on the working electrode to undergo reduction reaction, oxidation reaction occurs when the metal returns to the positive electrode part, the deposition is stripped, the response current of the electrode in electrochemical process is obtained, and the electrode potential and the response current in the process are recorded, so that a corresponding current-voltage curve is obtained. The inhibitor content can be measured indirectly by integrating the curve and calculating the charge required to strip the metal deposit.

The specific analysis steps of the inhibitor in the sample to be tested are as follows:

1, reagent:

The reference electrolyte VIRGIN MAKE-up Solution, VMS, is a cobalt plating bath without any organic additives, typically comprising cobalt salts, boric acid and sodium chloride, at concentrations consistent with the concentrations of the major components of the bath sample.

Additive standard solutions are known for calibration and standard curve establishment.

2 Endpoint determination three electrode system

Working electrode, rotating 2mm platinum disk electrode, mainly researching electrode;

a calomel electrode for providing stable reference potential and measuring the potential of the working electrode;

The counter electrode, the platinum sheet electrode and the working electrode form a loop to provide a current path.

3 Analysis step

Preparing VMS, wherein the solution contains cobalt ion 3g/L and boric acid 30g/L, pH =3.0;

Measurement of calibration factor the peak area Ar0 was recorded for the reference electrolyte by using an electrochemical workstation. Adding a standard solution of an inhibitor with known concentration into a reference electrolyte for at least 3 times, wherein the concentration is C, the volume is V, the cyclic voltammetry scanning is carried out, the peak area is recorded, and the Ar/Ar0 value is calculated and recorded as an end point.

Calculating a calibration factor:

Wherein:

c _end the inhibitor concentration at the end, i.e. the calibration factor;

standard inhibitor concentration;

v: inhibitor addition volume;

V _VMS reference electrolyte volume.

Sample measurement the pretreated cobalt plating solution sample was diluted with DI water to the appropriate concentration range to ensure that Ar/Ar0 was less than end value. And measuring the Ar0 of the basic electrolyte, adding the sample solution for a plurality of times, drawing an Ar/Ar 0-inhibitor addition standard curve, and calculating a linear regression equation.

Calculating the inhibitor concentration in the sample:

wherein;

C _end calibration factor

V. when c=c _end, the addition amount of inhibitor L

V _VMS volume of base electrolyte L

By using the cyclic voltammetry CVS of the calibration factor method, the content of the inhibitor in the cobalt plating solution can be accurately measured, which is helpful for optimizing the plating solution formulation and ensuring the quality and consistency of the plating layer.

As shown in fig. 1 to 6, the online analysis instrument for cobalt-plated inorganic matters and organic matters according to the embodiment of the application comprises a PLC control terminal 100 and a test case 900 for controlling the online analysis instrument, wherein the PLC control terminal 100 is respectively and electrically connected with a colorimetric analysis unit 500, a titration analysis unit 600, a CVS analysis unit 800, a sampling unit one 200 and a sampling unit two 300 in a bidirectional manner, an analysis chamber 901 and a sampling chamber 903 are respectively arranged at the upper end and the lower end of an inner cavity of the test case 900, wherein an analysis test module is integrally arranged in the inner cavity of the analysis chamber 901, and a sampling module is integrally arranged in the inner cavity of the sampling chamber 903;

The middle section of the surface of the test case 900 is also provided with a collecting chamber 902, and the collecting chamber 902 is used for placing other auxiliary devices during the test of the cobalt-plated inorganic and organic substances on-line analysis instrument;

Meanwhile, the sampling module comprises a first sampling unit 200 and a second sampling unit 300, wherein the first sampling unit 200 is used for sampling and analyzing the contrast color analysis unit 500 and the titration analysis unit 600, and the second sampling unit 300 is used for analyzing the liquid supply of the CVS analysis unit 800;

The first sampling unit 200 includes a first sampling pump 210, a first defoaming channel 220, and a first tank fluid chamber 230, where the first tank fluid chamber 230 is used for storing tank fluid, and an output end of the first tank fluid chamber 230 is connected to an input end of the first sampling pump 210 through a pipeline, and at the same time, an output end of the first sampling pump 210 is connected to an input end of the first defoaming channel 220 through a pipeline for defoaming the tank fluid, and an output end of the first defoaming channel 220 is connected to an input end of the first tank fluid chamber 230, so that the defoamed solution is sent into the first tank fluid chamber 230 for storage.

The second sampling unit 300 includes a second sampling pump 310, a second defoaming channel 320, and a second tank chamber 330, where the second tank chamber 330 is used for storing tank liquid, and an output end of the second tank chamber 330 is connected to an input end of the second sampling pump 310 through a pipeline, and at the same time, an output end of the second sampling pump 310 is connected to an input end of the second defoaming channel 320 through a pipeline for defoaming the tank liquid, and an output end of the second defoaming channel 320 is connected to an input end of the second tank chamber 330, so that the defoamed solution is sent into the second tank chamber 330 for storage.

Thus, the first tank 230 and the second tank 330 store different reagent solutions after defoaming, respectively.

The analytical test module and the sampling module are added with liquid through the multi-channel liquid supply valve group 400, the multi-channel liquid supply valve group 400 comprises a multi-channel valve I401 and a multi-channel valve II 402, wherein the output end of the multi-channel valve I401 is communicated with a sampling pump III 430, the output end of the sampling pump III 430 is communicated with the input end of the colorimetric analysis unit 500 through a pipeline and is used for conveying the sampled solution into the colorimetric analysis unit 500 for testing, the output end of the multi-channel valve II 402 is communicated with a sampling pump eight 440, and the output end of the sampling pump eight 440 is communicated with the input end of the CVS analysis unit 800 through a pipeline and is used for conveying the sampled solution into the CVS analysis unit 800 for analysis and testing.

The multi-channel liquid supply valve set 400 further comprises a standard sample part 410 and a pure water part 420, wherein the standard sample part 410 and the pure water part 420 are two groups, the standard sample part 410 is used for storing a solution standard sample, the pure water part 420 is used for storing pure water, meanwhile, the output ends of the first group of standard sample parts 410 and the pure water part 420 are respectively communicated with the input end of the multi-channel valve one 401 through pipelines, and the output ends of the second group of standard sample parts 410 and the pure water part 420 are respectively communicated with the output end of the multi-channel valve two 402 through pipelines.

In this way, under the action of the first multi-channel valve 401, the solutions in the first sampling unit 200, the second sampling unit 300, the standard sample portion 410 and the pure water portion 420 can be respectively sent into the first multi-channel valve 401, and then sent into the colorimetric analysis unit 500 through the first multi-channel valve 401 and the third sampling pump 430;

Under the action of the second multi-channel valve 402, the solutions in the first sampling unit 200, the second sampling unit 300, the standard sample part 410 and the first pure water part 420 can be sent into the second multi-channel valve 402 through pipelines, and then sent into the CVS analysis unit 800 for analysis and test through the eighth sampling pump 440.

The analysis test module comprises a colorimetric analysis unit 500, a titration analysis unit 600 and a CVS analysis unit 800 which are matched for use and are used for accurately analyzing the groove liquid, wherein the colorimetric analysis unit 500, the titration analysis unit 600 and the CVS analysis unit 800 are integrally arranged in an analysis chamber 901;

specifically, the inorganic test in the analysis test module comprises colorimetric analysis calibration and titration analysis calibration;

the input end of the colorimetric analysis unit 500 is communicated with a sampling pump IV 510 through a pipeline, the input end of the sampling pump IV 510 is communicated with a standard solution part 520 through a pipeline, and the output end of the standard solution part 520 and the input end of the sampling pump IV 510 are mutually communicated, so that the standard solution in the standard solution part 520 can be pressurized and rapidly fed into the colorimetric analysis unit 500 through the sampling pump IV 510

The colorimetric analysis unit 500 is communicated with a first cleaning and waste discharging part 540 through a pipeline, and a first electromagnetic valve 530 is arranged on the pipeline between the first cleaning and waste discharging part 540 and the colorimetric analysis unit 500 for switching on and off the pipeline between the contrast color analysis unit 500 and the first cleaning and waste discharging part 540;

The input end of the titration analysis unit 600 is communicated with a sampling pump seven 610 through a pipeline, the input end of the sampling pump seven 610 is communicated with a titration standard liquid part 620 through a pipeline, and the output end of the titration standard liquid part 620 and the input end of the sampling pump seven 610 are communicated with each other, so that the standard liquid in the titration standard liquid part 620 can be pressurized by the sampling pump seven 610 and rapidly fed into the titration analysis unit 600

The titration analysis unit 600 is communicated with a second cleaning drain portion 640 through a pipeline, and a second electromagnetic valve 630 is arranged on the pipeline between the second cleaning drain portion 640 and the titration analysis unit 600 in order to switch on and off the pipeline between the titration analysis unit 600 and the second cleaning drain portion 640;

The input end of the titration analysis unit 600 is further communicated with a sampling pump six 650 through a pipeline, wherein the input end of the sampling pump six 650 is communicated with the output end of the auxiliary reagent part 660 through a pipeline.

The colorimetric analysis unit 500 and the titration analysis unit 600 are communicated with each other through a pipeline, the input end of the sampling pump 700 is communicated with the second pure water part 710, and the output end of the sampling pump 700 is respectively communicated with the colorimetric analysis unit 500 and the titration analysis unit 600 through pipelines, so that pure water in the second pure water part 710 is sent into the colorimetric analysis unit 500 and the titration analysis unit 600 through the sampling pump 700.

Wherein the first sampling pump 210 is a peristaltic pump for sampling the liquid in the first tank, and the liquid in the first tank chamber 230 is pumped to the first sampling unit 200;

Wherein the second sampling pump 310 is a peristaltic pump for sampling the liquid in the second tank, and the liquid in the second tank 330 is pumped to the second sampling unit 300;

the third sampling pump 430 is an analysis sampling pump, specifically a peristaltic pump or a diaphragm pump, and pumps the bath solution/standard sample to the colorimetric analysis unit 500;

The multi-channel valve I401 is 3 in and 1 out, and the sample injection of the standard sample part 410 and the pure water part I420 is switched sampling

The colorimetric analysis unit 500 comprises a colorimetric sensor for performing online analysis on the content of cobalt ions in the tank liquor;

the sampling pump IV 510 is a pulse peristaltic pump, and pumps the standard solution for calibration of the standard solution part 520 to the colorimetric analysis unit 500;

The sampling pump five 700 is a diaphragm pump, and pure water is pumped to the colorimetric analysis unit 500 and the titration analysis unit 600 for calibration and cleaning;

the first electromagnetic valve 530 is used for controlling the discharge of the waste liquid of the colorimetric analysis unit 500 after the colorimetric analysis is finished;

The sixth sampling pump 650 is a pulse peristaltic pump, and is used for pumping mannitol, which is an auxiliary reagent for boric acid titration analysis in the auxiliary reagent part 660;

The seventh sampling pump 610 is a pulse peristaltic pump, and pumps the titration standard solution in the titration standard solution part 620 to the titration analysis unit 600;

the second electromagnetic valve 630 is used for opening the second electromagnetic valve 630 to discharge waste liquid after the titration reaction is completed;

the titration analysis unit 600 comprises a pH composite electrode, a reaction cup, a kit, and a stirring device for titration analysis of boric acid.

The working steps of cobalt plating on-line analysis and inorganic test are as follows:

1. Calibration part

1 Colorimetric calibration

The contrast color sensor needs to be calibrated on line before analysis, and the specific calibration steps are as follows:

① Checking whether each pump is abnormal in use or not, and testing after removing bubbles in the pipeline;

② Starting a sampling pump five 700, pumping pure water for flushing, wherein the flushing time and the flushing times can be set, and simultaneously starting;

③ Starting a sampling pump IV 510, and extracting colorimetric calibration liquid 1 which can be pure water or solution with known cobalt ion content for rinsing, wherein the rinsing time can be set;

④ Testing the absorbance of the colorimetric calibration standard liquid 1;

⑤ Starting a sampling pump five 700, pumping pure water to clean a colorimetric sensor in the colorimetric analysis unit 500, wherein the cleaning time and the cleaning times can be set;

⑥ Manually replacing the standard solution, and repeating steps ②、③ and ④;

⑦ And optionally establishing a standard curve by 3-5 standard solutions to obtain a unitary linear equation, and completing calibration.

2 Titration analysis calibration

Before titration analysis, the pH electrode needs to be calibrated on line, and 2-point calibration is adopted, wherein the specific calibration steps are as follows:

① Checking whether the use of each pump is abnormal or not, and whether a pipeline leaks air or not;

② Starting a sampling pump five 700, pumping pure water to flush the electrode in the reaction cup, and starting a solenoid valve two 630 to discharge waste liquid after the flushing set time is reached;

③ Extracting the pH standard liquid 1 to a colorimetric analysis unit 500, and washing the pH electrode;

④ Judging whether the signal V1 of the pH standard sample 1 is correct or not, if yes, automatically recording the signal value of the pH standard sample 1 by the PLC control terminal 100, otherwise, starting an alarm program and giving alarm information;

⑤ Repeating steps ②、③ and ④;

And calculating a linear equation according to the signal values recorded twice, wherein the slope and the intercept of the pH=kx+B are within the stipulations, and if the slope and the intercept are within the stipulations, the calibration is completed, otherwise, the calibration steps are repeated.

2. Test part

① Turning on the first sampling pump 210, and sucking the tank liquid in the first tank liquid chamber 230 to rinse and reflux in the pipeline;

② Opening corresponding valve ports of the sampling pump III 430 and the multichannel valve I401, and quantitatively pumping the groove liquid in the groove liquid chamber I230 to the colorimetric analysis unit 500;

③ In the colorimetric analysis unit 500, the concentration of cobalt ions in the tank liquor passes through a colorimetric sensor to measure the real-time absorbance, a calibration curve is utilized, the concentration value is calculated by a system, and the concentration value is automatically recorded and stored, so that the colorimetric analysis unit 500 is tested;

④ The cell liquid passes through the colorimetric analysis unit 500 and then reaches the titration analysis unit 600;

⑤ The titration analysis unit 600 starts a pump to pump a proper amount of auxiliary reagent to obtain boric acid complex, achieves the weak acid strengthening effect, and records the volume of the solution in the reaction cup as V0 at the moment;

⑥ Stirring is started, titration is carried out by using a titration standard solution until the titration end point is reached, boric acid analysis is completed, the titration volume is recorded as V1, and the boric acid content is calculated according to the following formula.

⑦ After calculation, opening the second electromagnetic valve 630 to discharge wastewater, and recording and outputting the measured boric acid concentration value;

⑧ After analysis is completed, the first sampling pump 210 is reversed, the tank liquor in the pipeline is emptied, pure water is pumped to clean the sampling pipeline, and the cleaning times and the time can be set;

⑨ The sampling pipeline is cleaned, and meanwhile, a sampling pump five 700 is started to pump pure water for spray flushing, and the flushing time and the flushing times can be set;

⑩ Opening the second electromagnetic valve 630 to discharge waste;

⑪ The above ①~⑩ steps were repeated to test the bath in bath chamber two 330.

Specifically, the organic test in the analysis test module comprises a CVS analysis test;

The CVS analysis unit 800 is respectively communicated with a third pure water part 820 and a VMS storage part 840 through pipelines, wherein the output end of the third pure water part 820 is communicated with a ninth sampling pump 810 through a pipeline, the output end of the ninth sampling pump 810 is communicated with the input end of the CVS analysis unit 800 through a pipeline, the output end of the VMS storage part 840 is communicated with a tenth sampling pump 830 through a pipeline, and the output end of the tenth sampling pump 830 is communicated with the input end of the CVS analysis unit 800;

Thus, pure water in the third pure water part 820 can be supplied to the CVS analysis unit 800 by the sampling pump nine 810, and the solution in the VMS storage part 840 can be supplied to the CVS analysis unit 800 by the third pure water part 820 for analysis and test.

The CVS analysis unit 800 is connected with a third cleaning and waste discharging part 860 through a pipeline, a third electromagnetic valve 850 is installed on the pipeline on the surface of the third cleaning and waste discharging part 860, and the third electromagnetic valve 850 is used for controlling the on-off of the pipeline on the third cleaning and waste discharging part 860.

The eight 440 of the sampling pump is matched with the second multi-channel valve 402 and is used for sampling switching of the standard sample part 410 and the first pure water part 420;

The sampling pump eight 440 is a high-precision injection pump for pumping the bath solution to the CVS analysis unit 800;

the sampling pump nine 810 is a diaphragm pump, and pure water in the pure water part three 820 is pumped to the CVS analysis unit 800 for calibration and cleaning;

the sampling pump ten 830 is a high-precision syringe pump, and pumps the base liquid VMS for diluting the sample in the VMS storage 840;

After the CVS analysis unit 800 is tested, the solenoid valve III 850 is opened to discharge waste liquid;

the CVS analysis Unit 800 contains a three electrode test System and reaction cup and its complement.

The cobalt plating online analysis organic test working steps are as follows:

CVS analysis preparation

Before titration analysis, the state of each electrode of the CVS three-electrode system needs to be checked and the injection pump needs to be calibrated, and the specific steps are as follows:

I electrode status inspection:

① The working electrode ensures the smoothness of the surface of the electrode and avoids the scratch on the surface or the mechanical operation of the electrode;

② The reference electrode needs to periodically supplement the internal reference and the external reference of the reference solution to ensure no bubbles;

③ The counter electrode ensures that the surface of the electrode is smooth and flat and has no adhesion.

II, calibrating a syringe pump:

① Selecting a syringe pump number at a calibration interface by using an online analysis software system, preparing an electronic level and a beaker, and peeling the beaker in advance;

② Clicking a starting button to reset the injection pump, and automatically stopping after resetting;

③ Setting the pulse number, clicking to start, switching to a water inlet valve port, enabling the injection pump to pump a fixed volume of pure water, and then exhausting to ensure that no bubbles exist in the liquid;

④ When the operation state of the injection pump prompts the next action, the pure water discharged by the injection pump is taken in through the beaker at the water outlet, and when the water containing volume of the beaker is about 10mL, clicking is stopped;

⑤ Obtaining pure water weight by using an electronic balance, wherein the density of the corresponding volume pure water is 1g/cm < 3 >;

⑥ Repeat step ②~⑤, measure the average 10 times in parallel;

The average value is input into a correction part volume frame, the current pulse number corresponds to the volume at the moment, and the calibration is completed.

And (3) an organic test step:

① A sampling pump ten 830 is opened to pump a base liquid VMS rinsing pipeline in the VMS storage part 840, and after the completion, waste liquid is discharged;

② The additive calibration calculates a calibration factor that a sampling pump ten 830 extracts quantitative VMS to a CVS analysis unit 800, and a three-electrode system performs cyclic voltammetry scanning and records the peak area Ar0 of the VMS. The sampling pump eight 440 extracts the quantitative tank liquor standard sample for many times, the concentration is C, the volume is V, the peak recording area Ar, ar/Ar0 after each time of adding is measured, and the process is stopped when the set end value is less than 1. Calculating a calibration factor:

③ Analyzing the bath solution, namely, after the sampling pump ten 830 extracts VMS to measure Ar0, adding quantitative unknown concentration bath solution for multiple times. And measuring Ar/Ar0 after each addition, and stopping adding the bath solution when the end value is reached. Calculating the concentration of the unknown tank liquor:

The same VMS, ar0 is the same, the same inhibitor, ar effect is the same. Therefore, the unknown concentration of the inhibitor in the tank liquor can be detected by using a calibration factor Cend obtained by the standard liquor, and the measured concentration value of the additive is recorded and output;

④ After the calculation is completed, the electromagnetic valve III 850 is opened to discharge the waste liquid.

Specifically, the on-line analysis instrument prompt of cobalt-plated inorganic matters and organic matters

The system sounds an alarm and displays alarm information when the following conditions occur during the test.

① The first sampling pump 210 and the second sampling pump 310 do not pump the tank liquor when performing the sampling step, and prompt the flow breaking alarm;

② Executing analysis process colorimetric, titration and CVS, wherein the analysis time exceeds a set value, and prompting overtime alarm;

③ The test value exceeds the set upper limit or is lower than the lower limit, and the warning of the overrun of the result is given out:

④ For reagents, standard solutions, pure water and the like used in analysis, if the liquid level in the storage container is lower than a set value, prompting low liquid level alarm;

⑤ The liquid level in the container for storing the waste liquid is higher than a set value, prompting high liquid level alarm;

⑥ The analysis instrument has a self-checking function, and prompts and alarms if the analysis instrument is not executed according to the setting;

⑦ After the calibration is finished, the on-line/manual calibration is not performed in time, and the alarm is prompted;

⑧ When the key components reach the service life, the maintenance alarm is prompted.

Specifically, the function of the cobalt-plated inorganic and organic on-line analysis instrument is as follows:

① The device can be in butt joint with an automatic dosing unit, and the dosing unit is controlled to automatically add solution containing boric acid, cobalt ions and additives according to an analysis result;

② The device realizes automatic adjustment of the addition amount according to the continuous multiple analysis results, so that the process parameters are more stable;

③ The device uses the Ethernet TCP/IP network communication to upload analysis, dosing and alarm information to a client MES system according to the Modbus protocol;

④ The device analysis system is automatically cleaned;

⑤ The device performs fixed-point analysis and external trigger analysis;

⑥ The device has multiple fool-proof alarm functions;

⑦ The device can store and export analysis, dosing and alarm information.

The above embodiments of the present application are only examples, and are not intended to limit the scope of the present application, and various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application. It should be noted that like reference numerals and letters refer to like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.

The foregoing is merely illustrative embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think about variations or substitutions within the technical scope of the present application, and the application should be covered. Therefore, the protection scope of the application is subject to the protection scope of the claims.

Claims (10)

1. An on-line analysis instrument for cobalt-plated inorganic matters and organic matters, which is characterized by comprising:

the PLC control terminal (100) and a testing machine box (900) for controlling an online analysis instrument, wherein an analysis chamber (901) and a sampling chamber (903) are respectively arranged at the upper end and the lower end of an inner cavity of the testing machine box (900), an analysis testing module is integrally arranged in the inner cavity of the analysis chamber (901), and a sampling module is integrally arranged in the inner cavity of the sampling chamber (903);

The analysis and test module comprises a colorimetric analysis unit (500), a titration analysis unit (600) and a CVS analysis unit (800), which are matched for use and are used for accurately analyzing the groove liquid;

Meanwhile, the sampling module comprises a first sampling unit (200) and a second sampling unit (300), the first sampling unit (200) is used for sampling and analyzing the colorimetric analysis unit (500) and the titration analysis unit (600), and the second sampling unit (300) is used for carrying out liquid supply analysis on the CVS analysis unit (800).

2. The on-line analysis instrument according to claim 1, wherein the first sampling unit (200) comprises a first sampling pump (210), a first defoaming channel (220) and a first tank chamber (230), wherein the first tank chamber (230) is used for storing tank liquid, and an output end of the first tank chamber (230) is in communication with an input end of the first sampling pump (210) through a pipeline, and at the same time, an output end of the first sampling pump (210) is in communication with an input end of the first defoaming channel (220) through a pipeline, and an output end of the first defoaming channel (220) is in communication with an input end of the first tank chamber (230).

3. The on-line analysis instrument for cobalt-plated inorganic matters and organic matters according to claim 2, wherein the second sampling unit (300) comprises a second sampling pump (310), a second defoaming channel (320) and a second tank chamber (330), wherein the second tank chamber (330) is used for storing tank liquid, and an output end of the second tank chamber (330) is communicated with an input end of the second sampling pump (310) through a pipeline, and meanwhile, an output end of the second sampling pump (310) is communicated with an input end of the second defoaming channel (320) through a pipeline, and an output end of the second defoaming channel (320) is communicated with an input end of the second tank chamber (330).

4. The online analysis apparatus for cobalt-plated inorganic and organic matters according to claim 3, wherein the liquid feeding is increased between the analysis and test module and the sampling module through a multi-channel liquid feeding valve group (400), and the multi-channel liquid feeding valve group (400) comprises a multi-channel valve I (401) and a multi-channel valve II (402), wherein the output end of the multi-channel valve I (401) is communicated with a sampling pump III (430), and the output end of the multi-channel valve II (402) is communicated with a sampling pump eight (440).

5. The apparatus for on-line analysis of cobalt-plated inorganic and organic matters according to claim 4, wherein the multi-channel liquid supply valve block (400) further comprises a standard sample part (410) and a pure water part (420), wherein the standard sample part (410) and the pure water part (420) are two groups, the standard sample part (410) is used for storing a solution standard sample, and the pure water part (420) is used for storing pure water.

6. The on-line analysis instrument for cobalt-plated inorganic matters and organic matters according to claim 5, wherein an input end of the colorimetric analysis unit (500) is communicated with a sampling pump IV (510) through a pipeline, and an input end of the sampling pump IV (510) is communicated with a standard solution part (520) through a pipeline;

The colorimetric analysis unit (500) is communicated with a first cleaning and waste discharging part (540) through a pipeline, and a first electromagnetic valve (530) is installed on the pipeline between the first cleaning and waste discharging part (540) and the colorimetric analysis unit (500).

7. The online analysis instrument for cobalt-plated inorganic matters and organic matters according to claim 6, wherein an input end of the titration analysis unit (600) is communicated with a sampling pump seven (610) through a pipeline, and an input end of the sampling pump seven (610) is communicated with a titration standard liquid part (620) through a pipeline;

The titration analysis unit (600) is communicated with a second cleaning liquid draining part (640) through a pipeline, and a second electromagnetic valve (630) is arranged on the pipeline between the second cleaning liquid draining part (640) and the titration analysis unit (600);

The input end of the titration analysis unit (600) is also communicated with a sampling pump six (650) through a pipeline, wherein the input end of the sampling pump six (650) is communicated with the output end of the auxiliary reagent part (660) through a pipeline.

8. The online analysis instrument for cobalt-plated inorganic matters and organic matters according to claim 7, wherein a sampling pump five (700) is communicated between the colorimetric analysis unit (500) and the titration analysis unit (600) through pipelines, the input end of the sampling pump five (700) is communicated with a pure water part two (710), and the output end of the sampling pump five (700) is respectively communicated with the colorimetric analysis unit (500) and the titration analysis unit (600) through pipelines.

9. The on-line analysis instrument for cobalt-plated inorganic matters and organic matters according to claim 8, wherein the CVS analysis unit (800) is respectively connected with a pure water portion three (820) and a VMS storage portion (840) through a pipeline, wherein an output end of the pure water portion three (820) is connected with a sampling pump nine (810) through a pipeline, and an output end of the VMS storage portion (840) is connected with a sampling pump ten (830) through a pipeline.

10. The on-line analysis instrument for cobalt-plated inorganic matters and organic matters according to claim 9, wherein the CVS analysis unit (800) is communicated with a cleaning waste discharge part III (860) through a pipeline, a solenoid valve III (850) is installed on the pipeline on the surface of the cleaning waste discharge part III (860), and the solenoid valve III (850) is used for controlling the on-off of the pipeline on the cleaning waste discharge part III (860).