CN217820011U - Continuous detection device for hydrogen peroxide concentration in acid cleaning liquid for wafers - Google Patents
Continuous detection device for hydrogen peroxide concentration in acid cleaning liquid for wafers Download PDFInfo
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- CN217820011U CN217820011U CN202221591472.5U CN202221591472U CN217820011U CN 217820011 U CN217820011 U CN 217820011U CN 202221591472 U CN202221591472 U CN 202221591472U CN 217820011 U CN217820011 U CN 217820011U
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Abstract
The utility model provides a hydrogen peroxide concentration continuous detection device in wafer acid cleaning solution, it can be arranged in the measuring of hydrogen peroxide concentration in the acid cleaning agent after the washing, and can detect in succession, detects weak point consuming time, can effectively improve detection efficiency. The device comprises a sample conveying pump for conveying a sample, and further comprises a color developing agent conveying pump, a reaction color developing unit, a color developing sample conveying pump, a light splitting and colorimetric unit A, a light splitting and colorimetric unit B and a densimeter; the sample delivery pump is connected with a sample inlet of the reaction color development unit, the color development agent delivery pump is connected with a color development agent inlet of the reaction color development unit, an outlet of the reaction color development unit is connected with the color development sample delivery pump, and the color development sample delivery pump is respectively connected with an inlet of the spectral colorimetric unit A and an inlet of the spectral colorimetric unit B through a first three-way valve; the densimeter is connected with a sample delivery pump.
Description
Technical Field
The utility model relates to a material concentration detection technical field specifically is a hydrogen peroxide concentration continuous detection device in wafer acid cleaning solution.
Background
In a wafer cleaning process, a frequently used sulfuric acid and hydrogen peroxide mixed solution is used as a cleaning agent for surface organic matters and residual metals in the cleaning process, the cleaning agent generally contains 40-75 wt% of sulfuric acid and 1-10 wt% of hydrogen peroxide, the concentration is high, the high-concentration sulfuric acid and hydrogen peroxide are still kept in a waste liquid after cleaning, if the waste acid cleaning agent needs to be recycled, the hydrogen peroxide needs to be removed firstly, and the residual sulfuric acid has recycling value, so the specific concentration of the hydrogen peroxide needs to be measured firstly, and the currently adopted method is mainly an electrode titration method, a pH electrode is adopted to titrate the sulfuric acid by sodium hydroxide, and a redox electrode is adopted to titrate the hydrogen peroxide by a cerium sulfate solution.
SUMMERY OF THE UTILITY MODEL
To detect the problem that hydrogen peroxide concentration consumes time long at present, the utility model provides a hydrogen peroxide concentration continuous detection device in wafer acid cleaning solution, it can be arranged in the detection of hydrogen peroxide concentration in the acid cleaning agent after wasing, and can detect in succession, detects weak point consuming time, can effectively improve detection efficiency.
The technical scheme is as follows: a continuous detection device for the concentration of hydrogen peroxide in a wafer acid cleaning solution comprises a sample delivery pump for delivering samples, a color developing agent delivery pump, a reaction color developing unit, a color developing sample delivery pump, a light splitting and colorimetric unit A, a light splitting and colorimetric unit B and a densimeter; the sample delivery pump is connected with a sample inlet of the reaction color development unit, the color development agent delivery pump is connected with a color development agent inlet of the reaction color development unit, an outlet of the reaction color development unit is connected with the color development sample delivery pump, and the color development sample delivery pump is respectively connected with an inlet of the spectral colorimetric unit A and an inlet of the spectral colorimetric unit B through a first three-way valve; the densimeter is connected with a sample delivery pump.
Preferably, the device further comprises a dilution water delivery pump, and the dilution water delivery pump is connected with a dilution water inlet of the reaction developing unit.
Preferably, the device further comprises a detergent delivery pump, and the detergent delivery pump is respectively connected with the inlet of the spectral colorimetric unit A and the inlet of the spectral colorimetric unit B through a second three-way valve.
Preferably, the reaction color developing unit includes a cup-shaped reaction vessel into which a sample tube, a dilution water tube, and a color developing agent tube are inserted, respectively, a sample transfer pump connected to the sample tube, a dilution water transfer pump connected to the dilution water tube, and a color developing agent transfer pump connected to the color developing agent tube.
Preferably, a stirring device is arranged in the reaction color development unit.
Preferably, the stirring device is a magnetic stirrer arranged at the bottom of the reaction color development unit, and the color development sample delivery pump is connected with an overflow port at the top of the reaction color development unit.
Preferably, the sample delivery pump, the developer delivery pump, the dilution water delivery pump, and the detergent delivery pump are peristaltic pumps.
Has the advantages that: the sample and the color developing agent are conveyed to the reaction color developing unit through the sample conveying pump and the color developing agent conveying pump to be mixed, the mixture is conveyed to the light splitting colorimetric unit through the color developing sample conveying pump, the light absorption value of the color developing sample is measured through the light splitting colorimetric unit, the densimeter is used for measuring the density of the sample, the concentration of the hydrogen peroxide can be obtained through calculation, the analysis time of the hydrogen peroxide is 30-60 minutes longer than that of a common hydrogen peroxide detection device, the analysis result time of the hydrogen peroxide detection device is within 5 minutes, the detection time is 6-12 times faster than that of the common detection device, and meanwhile when one light splitting colorimetric unit is cleaned, the hydrogen peroxide can be detected through the other light splitting colorimetric unit, so that continuous detection can be realized, and the detection efficiency is improved.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Detailed Description
As shown in fig. 1, the device for continuously detecting the concentration of hydrogen peroxide in a wafer acidic cleaning solution comprises a sample delivery pump 1 for delivering a sample, and further comprises a color developing agent delivery pump 2, a reaction color developing unit 3, a color developing sample delivery pump 4, a spectral colorimetric unit a, a spectral colorimetric unit B and a densimeter; the import of sample delivery pump 1 is connected with the waste liquid collecting vat of storage sample, export and reaction color development unit 3's sample access connection, the 2 intakes of color development agent delivery pump are connected with the medicament groove of storage color development agent, export and reaction color development unit 3's color development agent access connection, reaction color development unit 3's export and color development sample delivery pump 4 are connected, color development sample delivery pump's delivery outlet C passes through three-way valve one (not shown in the figure) respectively with the import D of spectral colorimetric unit A, spectral colorimetric unit B's import E is connected, the light-absorption value of color development sample is surveyed through the spectral colorimetric unit, the densimeter also is connected with sample delivery pump 1, be arranged in the sample input densimeter with in the waste liquid collecting vat and survey sample density.
In addition, in order to dilute the hydrogen peroxide concentration, the device also comprises a dilution water delivery pump 5, and the dilution water delivery pump 5 is connected with a dilution water inlet of the reaction developing unit 3, so that the concentration of the developed sample in the reaction developing unit can be diluted by injecting dilution water according to needs. The reaction color development unit 3 specifically comprises a cup-shaped reaction container, wherein a sample cannula, a dilution water cannula and a color development agent cannula are respectively inserted into the reaction container, a sample delivery pump 1 is connected with the sample cannula, a dilution water delivery pump 5 is connected with the dilution water cannula, a color development agent delivery pump 2 is connected with the color development agent cannula, a stirring device is arranged inside the reaction color development unit 3, the preferable magnetic stirring device can be a magnetic stirring rod 7 arranged at the bottom of the reaction color development unit 3, and a color development sample delivery pump 4 is connected with an overflow port 8 at the top of the reaction color development unit 3.
Meanwhile, in order to clean the spectral colorimetric unit conveniently, the device further comprises a detergent delivery pump 6, an inlet of the detergent delivery pump 6 is connected with a groove for storing detergent, and an outlet H of the detergent delivery pump is connected with an inlet F of the spectral colorimetric unit A and an inlet G of the spectral colorimetric unit B through a second three-way valve (not shown in the figure), so that the detergent is delivered to the spectral colorimetric unit A or the spectral colorimetric unit B to be cleaned as required.
The detection steps of the device are as follows: waste acidic cleaning solution: the concentration of hydrogen peroxide is 0 to 10wt%, the concentration of sulfuric acid is 0 to 75wt%, and the pH value is<0, density of 1000 to 1700kg/m 3 。
The waste acid cleaning solution is placed in a waste liquid collecting tank, is pumped into the detection device through a sample inlet by a sample delivery pump 1 at the flow rate of 0.8mL/min, and is delivered to a sample inlet of a reaction color development unit 3 through the sample delivery pump 1. The color developing agent is placed in the agent groove, the color developing agent delivery pump 2 pumps the color developing agent into the detection device through the color developing agent inlet at the flow rate of 0.2mL/min, and the color developing agent is delivered to the color developing agent inlet of the reaction color developing unit 3 through the color developing agent delivery pump 2. The color developing agent can be prepared by slowly adding 250-300mL and 96-98wt% concentrated sulfuric acid into 300-500ml deionized water, adding 20-50g of potassium titanium oxalate solid, heating to 70-90 ℃, keeping for 18-24 hours to completely dissolve the potassium titanium oxalate solid, naturally cooling to 20-30 ℃, standing for 24 hours, and filtering the color developing agent by using a 0.45 mu m TFE filter screen and filter paper to finally obtain the colorless clear color developing agent. The developer and the hydrogen peroxide generate a yellow-brown complex, the relation between the absorption brightness and the concentration of the complex accords with the Lamborber law, and the concentration of the hydrogen peroxide in the sample can be detected by a standard curve method. In addition, the dilution water can be added according to the needs (the quantity of the dilution water can be confirmed according to the concentration obtained by the first detection so as to keep the light absorption value in the optimal detection range during the spectrophotometric detection, and the actual concentration can be calculated according to the flow of the dilution water, the design can also complement the problem of narrow detection range in the complex color reaction, and can be suitable for the hydrogen peroxide concentration analysis with the concentration of 1mg/L to 100000mg/L or higher), the sample contacts with the color developing agent and the dilution water in the reaction color developing unit 3, and is quickly mixed and stirred by the magnetic stirrer 7 at the bottom of the color developing tank in the reaction color developing unit 3, and the retention time in the reaction color developing unit 3 reaches 3 minutes, so that the thorough mixing reaction is ensured. After reaction, the color development sample overflows from an overflow port 8 at the top of the reaction color development unit 3 and is conveyed by a color development sample conveying pump 4.
Then, the color development sample is conveyed to the three-way port through the color development sample conveying pump 4 at the flow rate of 1mL/min, the three-way port can be communicated with the light splitting and colorimetric unit A and the light splitting and colorimetric unit B, the color development sample is communicated with the light splitting and colorimetric unit A or B through the three-way port, a standby cleaning mode is carried out after each set of light splitting and colorimetric unit operates for one hour, and meanwhile, the three-way valve is controlled to be switched to another set of light splitting and colorimetric unit to operate and detect. The spectrocolorimetry unit is used for measuring the absorbance of a developed sample, and can be a common instrument for measuring the absorbance in the market, such as an absorbance detector (Jingyi photoelectricity), in the embodiment, an FX2000 spectrometer of Shanghai Shareye optics Co., ltd, an iDH2000-BSC deuterium halide two-in-one light source and an FVA-UV optical fiber adjustable attenuator are selected and purchased, the wavelength of the light source is controlled to be 400nm and R4 cuvette spectrum measurement supports, a 200ul light path 10mm two-way light threaded interface cup is used for fixing a cuvette, the cuvette is used as a colorimetric pipeline for containing sample liquid, the developed sample passes through the colorimetric pipeline in the spectrocolorimetry unit, the light source is controlled to be 400nm through the attenuator, after the developed sample passes through the light source, the 400nm absorbance value of the developed sample is detected through the spectrometer, and the hydrogen peroxide concentration can be converted according to linear regression through the absorbance value. The linear regression calibration curve of hydrogen peroxide is prepared by diluting a hydrogen peroxide standard product to five concentrations of 1, 5, 10, 25 and 50mg/L, adding 10g/L concentrated sulfuric acid into 50ml of the standard product, titrating by using a 0.1N potassium permanganate solution, wherein the titration end point is pink, the titration volume is A, deionized water is taken as a background value, titrating by using the 0.1N potassium permanganate solution, the titration end point is pink, the titration volume is B, and the hydrogen peroxide concentration is calculated as (A-B) × 0.1 × 340mg/L. And then pumping the five hydrogen peroxide with the calibrated concentration into a detection device one by one, carrying out color reaction analysis on a light absorption value according to the procedure, making a light absorption value-hydrogen peroxide concentration standard curve according to the concentration corresponding to the light absorption value, and taking the light absorption value-hydrogen peroxide concentration standard curve as a hydrogen peroxide concentration detection standard of the detection device, wherein a detection sample is compared with the curve to obtain the concentration after the light absorption value is detected by the device. And the color development sample is discharged from a waste liquid port after passing through the light-splitting colorimetric unit A or B.
And (3) the waste acid cleaning solution is placed in a waste liquid collecting tank, a sample peristaltic pump B pumps the waste acid cleaning solution into the detection device through a sample inlet at the flow rate of 10mL/min, the sample is conveyed to the inlet of a densimeter through a sample conveying pump, and the densimeter calculates the density of the sample through differential pressure detection conversion and corrects the density by temperature.
The hydrogen peroxide concentration (mg/L) and density of the sample were measured, and the hydrogen peroxide concentration (wt%) = (hydrogen peroxide concentration (mg/L)/density of the sample (kg/m) was calculated according to the following equation 3 ) /10000), the further sulfuric acid concentration can be converted by the following formula: sulfuric acid concentration (wt%) {3.46017E-15 (sample density- (0.0104028039) (hydrogen peroxide concentration (wt%)) 2 +3.4280969473 (hydrogen peroxide concentration (wt%)) -0.448534027)) 6 -2.84075E-11 [ (sample density of 0.0104028039) ]hydrogen peroxide concentration (wt%) ] 2 +3.4280969473 (hydrogen peroxide concentration (wt%)) -0.448534027)) 5 +9.64889E-08 [ ((sample density of- (0.0104028039) ] (hydrogen peroxide concentration (wt%)) 2 +3.4280969473 (hydrogen peroxide concentration (wt%)) -0.448534027)) 4 -1.73514E-04 (sample density- (0.0104028039 (hydrogen peroxide concentration (wt%)) 2 +3.4280969473 (hydrogen peroxide concentration (wt%)) -0.448534027)) 3 +1.74141E-01 (sample density- (0.0104028039) (hydrogen peroxide concentration (wt%)) 2 +3.4280969473 (hydrogen peroxide concentration (wt%)) -0.448534027)) 2 -9.22979E +01 (sample density- (0.0104028039.)) 2 +3.4280969473 (hydrogen peroxide concentration (wt%))/10000) -0.448534027) +2.01298E +04}.
When the water needs to be washed, pure water is placed in a pure water tank, the pure water is pumped into the detection device through the washing inlet by the washing delivery pump 6 at the flow rate of 3mL/min, the pure water is delivered to the three-way port through the washing delivery pump 6 and enters the light splitting and colorimetric unit in standby washing through the three-way port, and the pure water is washed by detergent after 15 minutes. And (3) placing the detergent in a detergent tank, pumping the detergent into the detection device through a detergent inlet by a washing delivery pump 6 at the flow rate of 1mL/min, delivering the detergent to the three-way port by the washing delivery pump 6, allowing the detergent to enter the spectral colorimetric unit to be cleaned in a standby mode through the three-way port, washing for 5 minutes by the detergent, and then cleaning for 15 minutes by using pure water. The detergent can clean the yellow complex, and avoids accumulated pollution on the tube wall of the colorimetric channel, which causes analysis errors. The preparation method of the detergent comprises the following steps of slowly adding 100mL of 25-32wt% concentrated sulfuric acid into 500-1000mL of deionized water, adding 10-30g of sodium citrate, stirring for 1-3 hours to completely dissolve the sodium citrate, standing for 24 hours, and filtering the detergent by using a 0.45 mu m PTFE filter screen and filter paper to finally obtain the colorless clear detergent.
After the device and the method are adopted, the following advantages are achieved: 1. compared with the common sulfuric acid and hydrogen peroxide detection device, the device can continuously analyze the samples for 30 to 60 minutes, the time difference between the analysis result and the samples in the sampling groove is within 5 minutes, and the detection time is 6 to 12 times faster than that of the common detection device.
2. Compared with the ultraviolet optical method, the device adopts the complex color reaction and the densimeter to be applicable to process acid or waste acid with different concentrations after formula conversion, and can avoid the impurity interference and the error caused by the concentration fluctuation of sulfuric acid and hydrogen peroxide.
3. In the detection device, the reaction unit adopts an own dilution system, the flow of dilution water can be adjusted in real time according to the detection concentration, so that the light absorption value is kept in the optimal detection range during the light splitting detection, and meanwhile, the actual concentration is calculated according to the flow of the dilution water. The design can also solve the problem of narrow detection range in the complex color reaction, and is suitable for the hydrogen peroxide concentration analysis of 1mg/L to 100000mg/L or higher.
4. In the detection device, the density can be directly and continuously detected by a densimeter detection method used for detecting the sulfuric acid, and then the concentration of the sulfuric acid is converted and calculated. Compared with the commonly used acid-base titration method, the analysis time is reduced by more than 99 percent, the manufacturing cost of the electrode used for the acid-base titration is high, the electrode is easy to damage, liquid alkali is required to be used as a titration reagent, and the densitometry detection method can avoid the problems. The analytical deviation was within. + -. 0.5%.
5. The inside unit of check out test set in this application adopts module unitization design, and is inside if single equipment trouble or damage, but quick replacement to can increase and decrease detecting element, conveying unit, reaction unit according to the detection demand, with satisfy different quality of water situations, and select suitable material to connect the liquid material as each unit, avoid taking place equipment corrosion situation.
6. The reaction color development unit that uses in this application adopts interior intubate rapid mixing stirring design, and the design of collocation top overflow can ensure that the reaction process is thorough, avoids producing short-flow and leads to the reaction or dilutes incompletely for detect the error.
7. The detergent used in the present application can clean the chromogenic complex, and prevent the complex precipitate from accumulating on the wall of the colorimetric channel to generate positive detection interference.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The utility model provides a hydrogen peroxide concentration continuous detection device in wafer acid cleaning solution which includes the sample delivery pump that is used for carrying the sample, its characterized in that: the device also comprises a color developing agent delivery pump, a reaction color developing unit, a color developing sample delivery pump, a spectral colorimetric unit A, a spectral colorimetric unit B and a densimeter; the sample delivery pump is connected with a sample inlet of the reaction color development unit, the color development agent delivery pump is connected with a color development agent inlet of the reaction color development unit, an outlet of the reaction color development unit is connected with the color development sample delivery pump, and the color development sample delivery pump is respectively connected with an inlet of the spectral colorimetric unit A and an inlet of the spectral colorimetric unit B through a first three-way valve; the densimeter is connected with a sample delivery pump.
2. The apparatus for continuously detecting the concentration of hydrogen peroxide in an acidic cleaning solution for wafers as claimed in claim 1, wherein: the device also comprises a dilution water delivery pump, and the dilution water delivery pump is connected with a dilution water inlet of the reaction color development unit.
3. The apparatus for continuously detecting the concentration of hydrogen peroxide in an acidic cleaning solution for wafers as claimed in claim 2, wherein: the device also comprises a detergent delivery pump, wherein the detergent delivery pump is respectively connected with the inlet of the spectral colorimetric unit A and the inlet of the spectral colorimetric unit B through a three-way valve II.
4. The apparatus for continuously detecting the concentration of hydrogen peroxide in an acidic cleaning solution for wafers as claimed in claim 2 or 3, wherein: the reaction color development unit is including being cupped reaction vessel, has inserted sample intubate, dilution water intubate and colour development agent intubate in it respectively, the sample delivery pump with the sample intubate is connected, the dilution water delivery pump with the dilution water intubate is connected, colour development agent delivery pump with colour development agent intubate is connected.
5. The apparatus for continuously detecting the concentration of hydrogen peroxide in an acidic cleaning solution for wafers as claimed in claim 4, wherein: and a stirring device is arranged in the reaction color development unit.
6. The apparatus for continuously detecting the concentration of hydrogen peroxide in an acidic cleaning solution for wafers as claimed in claim 5, wherein: the stirring device is a magnetic stirrer arranged at the bottom of the reaction color development unit, and the color development sample delivery pump is connected with an overflow port at the top of the reaction color development unit.
7. The apparatus for continuously detecting the concentration of hydrogen peroxide in an acidic cleaning solution for wafers as claimed in claim 3, wherein: the sample delivery pump, the color developing agent delivery pump, the color developing sample delivery pump, the dilution water delivery pump and the detergent delivery pump are peristaltic pumps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202221591472.5U CN217820011U (en) | 2022-06-24 | 2022-06-24 | Continuous detection device for hydrogen peroxide concentration in acid cleaning liquid for wafers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202221591472.5U CN217820011U (en) | 2022-06-24 | 2022-06-24 | Continuous detection device for hydrogen peroxide concentration in acid cleaning liquid for wafers |
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| CN217820011U true CN217820011U (en) | 2022-11-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202221591472.5U Active CN217820011U (en) | 2022-06-24 | 2022-06-24 | Continuous detection device for hydrogen peroxide concentration in acid cleaning liquid for wafers |
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| CN (1) | CN217820011U (en) |
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- 2022-06-24 CN CN202221591472.5U patent/CN217820011U/en active Active
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