A tmaH developing solution carbonic acid detection method, device and system

Abstract

The application relates to the technical field of developing solution carbon dioxide detection, in particular to a TMAH developing solution carbon dioxide detection method, device and system, which comprises the following steps: acquiring the PH value of a mixed solution in a titration process and the potential sequence of each electrode; acquiring a potential mutation site sequence set; acquiring the electrode position reliability of each mutation site sequence according to the discrete degree of all potential values corresponding to each mutation site sequence in the potential mutation site sequence set and the smooth degree of potential values in a preset time period before the potential mutation site sequence set; dividing the mutation site sequences in the potential mutation site sequence set into a first mutation cluster and a second mutation cluster; acquiring a first mutation time and a second mutation time according to the PH value and the electrode position reliability corresponding to each mutation site sequence; and acquiring the concentration of carbonate ions in the TMAH developing solution according to the difference between the hydrochloric acid consumption amounts corresponding to the second mutation time and the first mutation time. The application can more accurately acquire the time when the two potential transitions occur, and improves the detection precision of the carbonate ion concentration.

Description

Technical Field

[0001] The present application relates to the technical field of carbonic acid detection in developer solution, and in particular to a method, device and system for detecting carbonic acid in TMAH developer solution. Background Art

[0002] In semiconductor device manufacturing, the primary function of a developer is to dissolve the photoresist in the exposed areas, completely exposing the underlying substrate and forming the desired circuit pattern. Typically, the developer of choice is an aqueous solution of tetramethylammonium hydroxide (TMAH). To achieve precise etching of the photoresist, precise detection of the various components in the TMAH developer is essential.

[0003] During the preparation and use of TMAH developer, carbonate is incorporated. The concentration of carbonate affects the speed and effectiveness of development. If the concentration is too high, overdevelopment may occur, blurring the edges of the photolithographic pattern. If the concentration is too low, underdevelopment may occur, affecting the clarity of the photolithographic pattern. Therefore, the carbonate content in the TMAH developer must be continuously monitored during use to ensure its stability.

[0004] In the electronics industry, automated potentiometric titration is often used to determine the carbonate ion concentration in TMAH developer solutions. This method primarily relies on the consumption of the titrating acid solution during two potential transitions, using the chemical reaction equation for the reaction between the acid solution and carbonate ions to determine the carbonate ion concentration in the TMAH developer solution. However, in actual titrations, factors such as matrix effects and copolymers can lead to incomplete reaction between the acid solution and carbonate ions during titration, resulting in unclear potential transition signals and, ultimately, low accuracy in determining the carbonate ion concentration in TMAH developer solutions. Summary of the Invention

[0005] In order to solve the above technical problems, the purpose of this application is to provide a method, device and system for detecting carbonic acid in TMAH developer solution. The technical solutions adopted are as follows:

[0006] In a first aspect, an embodiment of the present application provides a method for detecting carbonic acid in a TMAH developer, the method comprising the following steps:

[0007] The pH value of the mixed solution of TMAH developer and hydrochloric acid and the potential value of each electrode are obtained in real time during the titration process; the sequence of all the potential values ​​of each electrode in the entire titration process in chronological order is recorded as the potential sequence of each electrode;

[0008] A potential mutation sequence set is obtained based on the intersection of the mutation point sequences in the potential sequences of all electrodes; the stationarity of each mutation sequence is obtained based on the trend and fluctuation of the potential values ​​of all mutation points corresponding to each mutation sequence in the preset time period, and the electrical position reliability of each mutation sequence is obtained based on the discreteness of all potential values ​​corresponding to each mutation sequence;

[0009] The mutation sequences in the potential mutation sequence set are divided into a first mutation cluster and a second mutation cluster according to the pH value corresponding to each mutation sequence; the titration coefficient of each mutation sequence is obtained based on the difference between the pH value corresponding to each mutation sequence in the potential mutation sequence set and the preset calibration pH value of the mutation cluster to which it belongs, as well as the electrochemical position reliability of each mutation sequence; the first mutation moment and the second mutation moment are obtained by comparing the titration coefficients of all mutation sequences in the first mutation cluster and the second mutation cluster with their preset thresholds; the concentration of carbonate ions in the TMAH developer is obtained based on the difference in hydrochloric acid consumption corresponding to the second mutation moment and the first mutation moment, the concentration of the hydrochloric acid standard titration solution, the molar mass of the carbonate particles, and the mass of the TMAH developer sample.

[0010] Preferably, the process of obtaining the potential mutation sequence set is as follows: recording the set consisting of the sequences corresponding to all mutation points in the potential sequence of each electrode as the mutation sequence set of each electrode; and recording the intersection of all mutation sequence sets as the potential mutation sequence set.

[0011] Preferably, the calculation formula for the stability of each mutation sequence is: , where represents the stability of the i-th mutation sequence, represents the mean value of the trend item strength of all mutation points corresponding to the i-th mutation position, represents the mean of the fluctuation factors of all mutation points corresponding to the i-th mutation position; wherein, the process of obtaining the trend item strength of each mutation point is as follows: the sequence composed of the potential values ​​in the preset time period before each mutation point is recorded as the potential subsequence of each mutation point, the potential subsequence corresponding to each mutation point is used as the input of the time series decomposition algorithm, and the output trend item strength is recorded as the trend item strength of each mutation point; the fluctuation factor of each mutation point refers to the average value of the distance between all potential values ​​in the potential subsequence of each mutation point and its fitting straight line.

[0012] Preferably, the calculation formula for the electrical position reliability of each mutation sequence is: Where, represents the electrical position confidence of the ith mutation sequence, norm( ) represents the normalization function, represents the stability of the i-th mutation sequence, represents the variance of the potential value corresponding to the ith mutation sequence in the potential sequence of all electrodes, is a preset constant.

[0013] Preferably, the specific process of dividing the mutation sequence in the potential mutation sequence set into the first mutation cluster and the second mutation cluster is: dividing the mutation sequence in the potential mutation sequence set with a pH value greater than a preset pH value into the first mutation cluster, and dividing the mutation sequence with a pH value less than or equal to the preset pH value into the second mutation cluster.

[0014] Preferably, the titration coefficient of each mutation sequence is calculated as follows: Where, represents the titration coefficient of the ith mutation sequence, represents the electrical position confidence of the ith mutation sequence, Indicates the pH value corresponding to the i-th mutation sequence, Indicates the preset calibration pH value of the mutation cluster where the i-th mutation sequence is located.

[0015] Preferably, the specific process of obtaining the first mutation time and the second mutation time is: recording the average of the times corresponding to all mutation sequences in the first mutation cluster that are greater than its preset threshold as the first mutation time; and recording the average of the times corresponding to all mutation sequences in the second mutation cluster that are greater than its preset threshold as the second mutation time.

[0016] Preferably, the calculation formula for the concentration of carbonate ions in the TMAH developer is: Where, Indicates the concentration of carbonate ions in TMAH developer, in mg / kg; and represents the hydrochloric acid consumption corresponding to the second mutation moment and the first mutation moment, respectively, in mL; c represents the concentration of the hydrochloric acid standard titration solution, in mol / L; M represents the molar mass value of the carbonate ion; and m represents the mass of the TMAH developer sample.

[0017] In a second aspect, an embodiment of the present application provides a TMAH developer carbonic acid detection device, the carbonic acid detection device comprising:

[0018] The carbonic acid detection device includes: a data acquisition module, a mutation characteristic analysis module, and a carbonate concentration measurement module.

[0019] Data acquisition module, used to obtain the pH value of the mixed solution and the potential value of each electrode during the titration process;

[0020] A mutation feature analysis module is used to obtain the electrical position reliability of each mutation sequence based on the trend and fluctuation of the potential values ​​in a preset time period before all mutation points corresponding to each mutation sequence, as well as the discreteness of all potential values ​​corresponding to each mutation sequence;

[0021] The carbonate concentration determination module is used to obtain the first mutation time and the second mutation time according to the pH value and the electrical position reliability corresponding to each mutation sequence, and then obtain the concentration of carbonate ions in the TMAH developer.

[0022] In a third aspect, an embodiment of the present application further provides a TMAH developer carbonic acid detection system, the system comprising a memory, a processor, and a computer program stored in the memory and running on the processor, wherein when the processor executes the computer program, the steps of any one of the above-mentioned TMAH developer carbonic acid detection methods are implemented.

[0023] As can be seen from the above embodiments, the method, device, and system for detecting carbonic acid in a TMAH developer provided by the embodiments of the present application have at least the following beneficial effects:

[0024] In the traditional automatic potentiometric titration of carbonate ion concentration in TMAH developer, the hydrochloric acid consumption corresponding to the mutation point of the potential curve is directly measured, and the hydrochloric acid consumption of the titration is measured to calculate the carbonate ion concentration in the developer. In the actual process, the copolymer is easily produced during the titration process, and the reaction during the titration is incomplete, so that the potential change of the potential curve and the actual titration solution is biased, affecting the accuracy value of carbonate detection. Thus, the application constructs an electric position confidence by analyzing the trend term change of the potential mutation point and the potential deviation between different electrodes during the titration process, and can accurately reflect the possibility that each mutation sequence is the potential transition moment; and then in combination with the pH value corresponding to each mutation sequence, the titration coefficient of each mutation sequence is obtained, and the accurate acquisition of the two potential transition moments in the titration process is achieved, and the difference of the hydrochloric acid consumption between the two potential transition moments is finally obtained. The concentration value of carbonate ions in TMAH developer is obtained using concentration calculation formula, which solves the problem that the traditional automatic titration method is easily affected by the degree of chemical reaction of the titration solution, and improves the accuracy of carbonate concentration detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions and advantages of the embodiments of the present application or the prior art, the following is a brief introduction to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0026] Figure 1 A flowchart of a method for detecting carbonic acid in a TMAH developer solution according to one embodiment of the present application is provided;

[0027] Figure 2 This is a schematic structural diagram of a TMAH developer carbonic acid detection device provided in an embodiment of the present application. DETAILED DESCRIPTION

[0028] To further illustrate the technical means and effectiveness of this application to achieve its intended purpose, the following, in conjunction with the accompanying drawings and preferred embodiments, describes in detail a method, device, and system for detecting carbonic acid in a TMAH developer solution, including its specific implementation, structure, features, and effectiveness. In the following description, references to "one embodiment" or "another embodiment" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.

[0029] Unless otherwise specified and limited, terms such as "comprises", "includes" or any other variants thereof are intended to cover non-exclusive inclusion, so that a circuit structure, article or device comprising a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such article or device. In the absence of further restrictions, an element defined by the sentence "comprises a ..." does not exclude the presence of other identical elements in the article or device comprising the element. In addition, the term "and\or" used herein includes any and all combinations of one or more related listed items. All technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs.

[0030] The following describes in detail a method, device and system for detecting carbonic acid in a TMAH developer provided by the present application with reference to the accompanying drawings.

[0031] See also Figure 1 , which shows a flow chart of a method for detecting carbonic acid in a TMAH developer provided by one embodiment of the present application, the method comprising the following steps:

[0032] Step 1: Real-time acquisition of the pH value of the mixed solution of TMAH developer and hydrochloric acid and the potential value of each electrode during the titration process; the sequence of all potential values ​​of each electrode in the entire titration process in chronological order is recorded as the potential sequence of each electrode.

[0033] In this application, m (in this example, m is 20) grams of TMAH developer solution were sampled from the developer tank. The minimum resolution of the electronic balance was required to be 0.0001 g. An automatic potentiometric titrator was used for titration, with a burette volume resolution of at least 1 / 10000 mL. Hydrochloric acid was used as the acidic solution for titration, and the following configurations were used in accordance with GB / T601: the concentration of hydrochloric acid standard titration solution 1 was 0.1 mol / L; the concentration of hydrochloric acid standard titration solution 2 was 1 mol / L. In this example, the ambient temperature for the titration was set at 22°C ± 2°C, and the relative humidity was maintained between 30% and 80%.

[0034] The titration steps of the titration device in this embodiment are as follows: m grams of TMAH developer sample is placed in a detection container, and a pH detection probe is placed in the detection container to obtain the pH value of the mixed solution of TMAH developer and hydrochloric acid in the detection container in real time. At the same time, four aqueous composite electrodes are placed at four positions of the detection container to obtain the potential value (conductivity) of the mixed solution in real time and initialize the automatic potentiometric titrator; because the pH value of developers produced by different manufacturers is inconsistent during preparation and use, and TMAH developer is strongly alkaline, it is necessary to pre-neutralize the TMAH developer with standard hydrochloric acid titration solution 2 in a closed environment to adjust the pH value of the TMAH developer to a uniform initial value. In this embodiment, the initial pH value is 11; then, standard hydrochloric acid titration solution 1 is used to titrate under closed conditions; when the pH value of the mixed solution is detected to be lower than 4, the titration is determined to be complete.

[0035] The sequence of all potential values ​​of each electrode in the entire titration process in chronological order is recorded as the potential sequence of each electrode.

[0036] It should be noted that all of the above sensors collect data at a fixed time interval, which in this embodiment is set to 0.5 s. Furthermore, during the titration process with the hydrochloric acid standard solution, the titration is performed using an automatic potentiometric titrator at a fixed flow rate, which in this embodiment is 1 mL / min.

[0037] Step 2: Obtain a potential mutation sequence set based on the intersection of the mutation point sequences in the potential sequences of all electrodes; obtain the stationarity of each mutation sequence based on the trend and fluctuation of the potential values ​​of all mutation points corresponding to each mutation sequence in the preset time period, and obtain the electrical position reliability of each mutation sequence based on the discrete degree of all potential values ​​corresponding to each mutation sequence.

[0038] Since the TMAH developer contains a certain amount of carbonate ions, there are usually four stages in the titration process, specifically:

[0039] Phase 1: Neutralization reaction: At this stage, since the TMAH developer is strongly alkaline and the pH value of the TMAH developer is adjusted to 11 after pretreatment, there are still a large number of hydroxide ions in the solution ( ), so with the addition of hydrochloric acid, hydroxide ions are consumed first, the pH value gradually decreases, and the potential value slowly rises. Due to the consumption of hydroxide ions, the hydrogen ion gradually increases, but the buffering effect suppresses the potential mutation. Therefore, no potential jump occurs at this stage.

[0040] Phase 2: Bicarbonate Generation: When the hydroxide ions in the mixed solution are completely consumed, the carbonate ions in the solution react with the hydrogen ions to produce bicarbonate ions, marking the first potential jump. The pH of the mixed solution at this stage will be slightly alkaline (around 8.0) and gradually decrease to acidic (around 5.0). As carbonate ions convert to bicarbonate ions, the hydrogen ion concentration rapidly increases, causing the electrode potential to increase rapidly. The magnitude of the jump is affected by the higher the carbonate concentration, and the more obvious the jump is.

[0041] Stage 3: Carbonation ; When all carbonate ions are converted into bicarbonate ions, hydrochloric acid is further added. At this time, hydrogen ions combine with bicarbonate ions to generate carbonic acid. At this time, a second potential transition will occur. At this stage, bicarbonate ions are further protonated to release carbon dioxide, so that the hydrogen ions jump again.

[0042] Stage 4: Simple hydrochloric acid titration. At this stage, the hydrogen ions in the solution are already saturated, so the potential rises gently and the potential response approaches a linear reaction.

[0043] Therefore, during the entire titration process, the concentration of carbonate ions in the developer can be calculated based on the volume difference between the hydrochloric acid consumption corresponding to the second potential transition and the first potential transition.

[0044] During the entire titration process, there will be two potential transition points in the potential change. However, since the reaction of hydrogen ions in the solution takes time and the uniformity of the reaction in the titration vessel may cause multiple potential jumps during the titration process, resulting in the positions of the two potential transition points finally obtained not corresponding to the actual reaction conditions, further affecting the determination of hydrochloric acid consumption during the titration process, thereby causing deviations in the detection of carbonate ions in the TMAH developer.

[0045] The aqueous composite electrode can be used to collect the potential of a small area in the titration vessel. Ideally, the potential changes at each location in the titration vessel are consistent. However, in practice, the copolymer and matrix effects may cause uneven reactions, resulting in time differences in the mutation points collected by the four-position electrode sensors in the titration vessel. Therefore, it is necessary to combine the potential series collected by each electrode during the entire titration process to analyze the actual mutation point situation. Therefore, it is necessary to obtain all potential mutation points during the entire titration stage.

[0046] Taking the potential sequence of a single electrode during the entire titration process as an example, a mutation point detection algorithm is used to obtain the mutation points. The set of bit sequences corresponding to all mutation points in the electrode's potential sequence is recorded as the mutation bit sequence set for the electrode. Among these, mutation point detection algorithms include, but are not limited to, the LOF algorithm, the isolation forest algorithm, and the BFAST algorithm. In this example, the LOF algorithm is selected, and the algorithm parameters are set to the default values.

[0047] Similarly, the same method as above is used to obtain the mutation sequence sets corresponding to the electrodes in the other three directions, and the intersection of the mutation sequence sets of all electrodes is used as the potential mutation sequence set in the titration process.

[0048] The following analysis uses a single mutation sequence in a potential mutation sequence set as an example. Before the corresponding mutation point appears, the potential value increases slowly due to the gradual increase in hydrogen ion concentration. A potential jump occurs only when the ions reacting with the hydrogen ions change. Consequently, the potential tends to be more robust and stable. However, when ions co-aggregate and the reaction is uneven, the potential changes exhibit a certain degree of random fluctuation, affecting the strength of the mutation point.

[0049] The sequence of potential values ​​within t seconds before each mutation point is recorded as the potential subsequence corresponding to each mutation point. This subsequence serves as the input to the time series decomposition algorithm, and the output trend item strength is recorded as the trend item strength at each mutation point. In this embodiment, t is set to 10; the user can set this value based on actual circumstances. The time series decomposition algorithm is well known in the art, and the specific process will not be described in detail here.

[0050] The potential subsequence at each mutation point is used as input for the least squares method to obtain a fitted straight line for the potential subsequence at each mutation point. The average distance between all potential values ​​in the potential subsequence at each mutation point and the fitted straight line is recorded as the fluctuation factor for each mutation point. A larger fluctuation factor indicates greater fluctuation in the potential values ​​in the potential subsequence at that mutation point. The least squares method is a well-known technique, and the specific process will not be described in detail here.

[0051] As a preferred embodiment, the stability of each mutation sequence is obtained based on the trend and fluctuation of the potential values ​​in a preset time period before all mutation points corresponding to each mutation sequence in the potential mutation sequence set, which is used to characterize the stability of the potential value at the position where each mutation sequence is located.

[0052] Based on the above analysis characteristics, the stationarity of a single mutation sequence is calculated: , where represents the stability of the i-th mutation sequence, represents the mean value of the trend item strength of all mutation points corresponding to the i-th mutation position, Represents the mean of the fluctuation factors of all mutation points corresponding to the i-th mutation position.

[0053] Therefore, when the mutation point of the i-th mutation sequence is a real and effective mutation point, the stronger the trend term of the potential value in its potential subsequence and the smaller the degree of fluctuation, the smaller the obtained fluctuation factor, and the higher the stability value of the mutation point.

[0054] In addition, the titration reaction may be uneven due to ion copolymerization during the titration process, and the potential deviation in each direction is large. When there is no ion copolymerization interference, the overall potential deviation in the titration solution is small.

[0055] Therefore, according to the stability of each mutation sequence and the discreteness of all potential values ​​corresponding to each mutation sequence, the electrical position reliability of each mutation sequence is obtained. In this embodiment, the electrical position reliability of the i-th mutation sequence is recorded as , its specific expression is: Where, represents the electrical position confidence of the ith mutation sequence, represents the stability of the i-th mutation sequence, represents the variance of the potential value corresponding to the ith mutation sequence in the potential sequence of all electrodes, is a preset constant used to prevent the denominator from being 0. In this embodiment, it is set to 0.01. norm() represents a normalization function. In this embodiment, the sigmoid function is used for normalization.

[0056] A larger electrical position confidence value indicates a higher probability that the mutation sequence represents the moment when two potential transitions occurred during the titration. For mutation sequences in the potential sequence caused by ion coagulation and reaction heterogeneity, the heterogeneity caused by ion coagulation will result in a greater dispersion of potential values ​​at different electrodes. Furthermore, the more unstable the potential values ​​of each electrode at that moment, the smaller the electrical position confidence value of the mutation sequence.

[0057] Step 3: Divide the mutation sequences in the potential mutation sequence set into a first mutation cluster and a second mutation cluster according to the pH value corresponding to each mutation sequence; obtain the titration coefficient of each mutation sequence based on the difference between the pH value corresponding to each mutation sequence in the potential mutation sequence set and the preset calibration pH value of the mutation cluster to which it belongs, as well as the electrochemical position reliability of each mutation sequence; obtain the first mutation time and the second mutation time by comparing the titration coefficients of all mutation sequences in the first mutation cluster and the second mutation cluster with their preset thresholds; obtain the concentration of carbonate ions in the TMAH developer solution based on the difference in hydrochloric acid consumption corresponding to the second mutation time and the first mutation time, as well as the concentration of the hydrochloric acid standard titration solution, the molar mass of the carbonate particles, and the mass of the TMAH developer solution sample.

[0058] Since the titration rate is fixed during the automatic potentiometric titration process, the hydrochloric acid consumption at the moment of the mutation point can be calculated through the time corresponding to the mutation point.

[0059] Based on prior knowledge, it can be determined that the pH value of the mixed solution is theoretically around 8 when the first potential transition occurs, and around 5 when the second potential transition occurs. Therefore, the pH values ​​corresponding to all mutation sequences in the potential mutation sequence set can be obtained. Mutation sequences in the potential mutation sequence set with pH values ​​greater than a preset pH value are grouped into the first mutation cluster, and mutation sequences with pH values ​​less than or equal to the preset pH value are grouped into the second mutation cluster. In this embodiment, the preset pH value is 6.5.

[0060] Furthermore, based on the difference between the pH value corresponding to each mutation sequence in the potential mutation sequence set and the preset calibrated pH value of the mutation cluster to which it belongs, as well as the electrical position reliability of each mutation sequence, the titration coefficient of each mutation sequence is obtained to characterize the possibility that each mutation sequence belongs to the potential transition moment.

[0061] In this embodiment, the titration coefficient of the i-th mutation sequence is recorded as , whose expression is: Where, represents the titration coefficient of the ith mutation sequence, represents the electrical position confidence of the ith mutation sequence, Indicates the pH value corresponding to the i-th mutation sequence, Indicates the preset calibration pH value of the mutation cluster where the i-th mutation sequence is located. In this embodiment, the preset calibration pH value of the first mutation cluster is set to 8, and the preset calibration pH value of the second mutation cluster is set to 5.

[0062] The larger the value of , the smaller the deviation between the pH value of the i-th mutation sequence and its calibrated pH value, and the greater the electric position confidence, then the mutation sequence is more likely to represent the true potential transition moment in the actual process; otherwise, it means that the mutation sequence may appear due to interference, and the cause of the mutation may be caused by interference.

[0063] The titration coefficient of each mutation sequence in the potential mutation sequence set can be obtained through the above method. Furthermore, according to the titration coefficient of the mutation sequence of each mutation cluster, the effective mutation time of each mutation cluster is obtained. The specific method is:

[0064] The titration coefficients of all mutation sequences in the first mutation cluster are used as the input of the Otsu threshold method, the segmentation threshold is input and recorded as the preset threshold, the time corresponding to the mutation sequence in the first mutation cluster greater than the preset threshold is recorded as the effective mutation time, and the average of all effective mutation times is recorded as the first mutation time.

[0065] Similarly, the second mutation moment is obtained according to the titration coefficients of all mutation sequences in the second mutation cluster.

[0066] Furthermore, the concentration of carbonate ions in the TMAH developer is calculated as follows: Where, Indicates the concentration of carbonate ions in TMAH developer, in mg / kg; and represents the hydrochloric acid consumption corresponding to the second mutation moment and the first mutation moment, respectively, in mL; c represents the concentration of the hydrochloric acid standard titration solution, in mol / L. Since the hydrochloric acid standard titration solution 1 is selected in the titration process, c=0.1 in this embodiment; M represents the molar mass value of the carbonate ion, which is 60.01; m represents the mass of the TMAH developer sample, which is 20 g in this embodiment.

[0067] The carbonate ion concentration in the TMAH developer sample was obtained through final titration. In addition, the sample was measured five times in parallel under the same conditions, and the average value of the carbonate ion concentration obtained from the five measurements was taken as the actual value of the carbonate ion concentration in the current TMAH developer.

[0068] See also Figure 2 , Figure 2 Schematic diagram of the structure of a TMAH developer carbonic acid detection device provided in an embodiment of the present application. In this embodiment, the terminal includes various units for executing various steps in an embodiment corresponding to a TMAH developer carbonic acid detection method. Figure 2 The carbonic acid detection device includes: a data acquisition module, a mutation feature analysis module, and a carbonate concentration determination module.

[0069] Data acquisition module, used to obtain the pH value of the mixed solution and the potential value of each electrode during the titration process;

[0070] A mutation feature analysis module is used to obtain the electrical position reliability of each mutation sequence based on the trend and fluctuation of the potential values ​​in a preset time period before all mutation points corresponding to each mutation sequence, as well as the discreteness of all potential values ​​corresponding to each mutation sequence;

[0071] The carbonate concentration determination module is used to obtain the first mutation time and the second mutation time according to the pH value and the electrical position reliability corresponding to each mutation sequence, and then obtain the concentration of carbonate ions in the TMAH developer.

[0072] Based on the same inventive concept as the above method, an embodiment of the present application also provides a TMAH developer carbonic acid detection system, including a memory, a processor, and a computer program stored in the memory and running on the processor. When the processor executes the computer program, the steps of any one of the above-mentioned TMAH developer carbonic acid detection methods are implemented.

[0073] The various embodiments in this application are described in a progressive manner, and the same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on the differences from other embodiments.

[0074] It should be noted that, unless otherwise specified and limited, terms such as "include", "comprising" or any other variations thereof are intended to cover non-exclusive inclusion, so that a circuit structure, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such article or device. In the absence of further restrictions, the phrase "including a ..." defines an element, does not exclude the presence of other identical elements in the article or device including the element. In addition, the term "and\or" used herein includes any and all combinations of one or more related listed items.

[0075] Those skilled in the art will readily appreciate other embodiments of the present application after considering the specification and practicing the invention herein. This application is intended to cover any variations, uses, or adaptations of the present application that follow the general principles of the present application and include common knowledge or customary techniques in the art not invented herein.

[0076] It will be understood that the present application is not limited to the exact construction that has been described above and shown in the drawings, and that various modifications and changes may be made without departing from the scope thereof.

Claims

1. A TMAH developer carbonic acid detection method, characterized in that, The method comprises the following steps: The pH value of the mixed solution of TMAH developer and hydrochloric acid and the potential value of each electrode are obtained in real time during the titration process; the sequence of all the potential values ​​of each electrode in the entire titration process in chronological order is recorded as the potential sequence of each electrode; A potential mutation sequence set is obtained based on the intersection of the mutation point sequences in the potential sequences of all electrodes; the stationarity of each mutation sequence is obtained based on the trend and fluctuation of the potential values ​​of all mutation points corresponding to each mutation sequence in the preset time period, and the electrical position reliability of each mutation sequence is obtained based on the discreteness of all potential values ​​corresponding to each mutation sequence; The mutation sequences in the potential mutation sequence set are divided into a first mutation cluster and a second mutation cluster according to the pH value corresponding to each mutation sequence; the titration coefficient of each mutation sequence is obtained based on the difference between the pH value corresponding to each mutation sequence in the potential mutation sequence set and the preset calibration pH value of the mutation cluster to which it belongs, as well as the electrochemical position reliability of each mutation sequence; the first mutation moment and the second mutation moment are obtained by comparing the titration coefficients of all mutation sequences in the first mutation cluster and the second mutation cluster with their preset thresholds; the concentration of carbonate ions in the TMAH developer is obtained based on the difference in hydrochloric acid consumption corresponding to the second mutation moment and the first mutation moment, the concentration of the hydrochloric acid standard titration solution, the molar mass of the carbonate particles, and the mass of the TMAH developer sample.

2. a TMAH developer carbonic acid detection method as claimed in claim 1, is characterized in that, The process of obtaining the potential mutation sequence set is as follows: recording the set consisting of the sequences corresponding to all mutation points in the potential sequence of each electrode as the mutation sequence set of each electrode; and recording the intersection of all mutation sequence sets as the potential mutation sequence set.

3. A TMAH developer carbonic acid detection method as claimed in claim 1, characterized in that, The calculation formula for the stability of each mutation sequence is: , where represents the stability of the i-th mutation sequence, represents the mean value of the trend item strength of all mutation points corresponding to the i-th mutation position, represents the mean of the fluctuation factors of all mutation points corresponding to the i-th mutation position; wherein, the process of obtaining the trend item strength of each mutation point is as follows: the sequence composed of the potential values ​​in the preset time period before each mutation point is recorded as the potential subsequence of each mutation point, the potential subsequence corresponding to each mutation point is used as the input of the time series decomposition algorithm, and the output trend item strength is recorded as the trend item strength of each mutation point; the fluctuation factor of each mutation point refers to the average value of the distance between all potential values ​​in the potential subsequence of each mutation point and its fitting straight line.

4. a TMAH developer carbonic acid detection method as claimed in claim 1, is characterized in that, The calculation formula of the electrical position reliability of each mutation sequence is: Where, represents the electrical position confidence of the ith mutation sequence, norm( ) represents the normalization function, represents the stability of the i-th mutation sequence, represents the variance of the potential value corresponding to the ith mutation sequence in the potential sequence of all electrodes, is a preset constant.

5. A TMAH developer carbonic acid detection method as claimed in claim 1, characterized in that, The specific process of dividing the mutation sequence in the potential mutation sequence set into the first mutation cluster and the second mutation cluster is: dividing the mutation sequence in the potential mutation sequence set with a pH value greater than the preset pH value into the first mutation cluster, and dividing the mutation sequence with a pH value less than or equal to the preset pH value into the second mutation cluster.

6. A TMAH developer carbonic acid detection method as claimed in claim 1, characterized in that, The calculation formula of the titration coefficient of each mutation sequence is: Where, represents the titration coefficient of the ith mutation sequence, represents the electrical position confidence of the ith mutation sequence, Indicates the pH value corresponding to the i-th mutation sequence, Indicates the preset calibration pH value of the mutation cluster where the i-th mutation sequence is located.

7. A TMAH developer carbonic acid detection method as claimed in claim 1, characterized in that, The specific process of obtaining the first mutation time and the second mutation time is as follows: the average of the times corresponding to all mutation sequences in the first mutation cluster that are greater than its preset threshold is recorded as the first mutation time; and the average of the times corresponding to all mutation sequences in the second mutation cluster that are greater than its preset threshold is recorded as the second mutation time.

8. A TMAH developer carbonic acid detection method as claimed in claim 1, characterized in that, The calculation formula for the concentration of carbonate ions in the TMAH developer is: Where, Indicates the concentration of carbonate ions in TMAH developer, in mg / kg; and represents the hydrochloric acid consumption corresponding to the second mutation moment and the first mutation moment, respectively, in mL; c represents the concentration of the hydrochloric acid standard titration solution, in mol / L; M represents the molar mass value of the carbonate ion; and m represents the mass of the TMAH developer sample.

9. A TMAH developer carbonic acid detection device, characterized in that: Implementing a method for detecting carbonic acid in a TMAH developer according to any one of claims 1 to 8, the carbonic acid detection device comprises: Data acquisition module, used to obtain the pH value of the mixed solution and the potential value of each electrode during the titration process; A mutation feature analysis module is used to obtain the electrical position reliability of each mutation sequence based on the trend and fluctuation of the potential values ​​in a preset time period before all mutation points corresponding to each mutation sequence, as well as the discreteness of all potential values ​​corresponding to each mutation sequence; The carbonate concentration determination module is used to obtain the first mutation time and the second mutation time according to the pH value and the electrical position reliability corresponding to each mutation sequence, and then obtain the concentration of carbonate ions in the TMAH developer.

10. A TMAH developer carbonic acid detection system, comprising a memory, a processor, and a computer program stored in the memory and running on the processor, characterized in that: When the processor executes the computer program, the method for detecting carbonic acid in a TMAH developer solution according to any one of claims 1 to 8 is implemented.

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