CN101567309A - Device for blending etching solution and device for determinating concetration of etching solution - Google Patents
Device for blending etching solution and device for determinating concetration of etching solution Download PDFInfo
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- CN101567309A CN101567309A CNA2009101331960A CN200910133196A CN101567309A CN 101567309 A CN101567309 A CN 101567309A CN A2009101331960 A CNA2009101331960 A CN A2009101331960A CN 200910133196 A CN200910133196 A CN 200910133196A CN 101567309 A CN101567309 A CN 101567309A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67075—Apparatus for fluid treatment for etching for wet etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
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- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
- G05D21/00—Control of chemical or physico-chemical variables, e.g. pH value
- G05D21/02—Control of chemical or physico-chemical variables, e.g. pH value characterised by the use of electric means
Abstract
The present invention provides a etching solution blending device which is used in a semiconductor manufacturing works or flat-panel display manufacturing works and is capable of constantly blending nitric acid concentration, moisture concentration, phosphoric acid concentration and acetic acid concentration of the etching solution. The device comprises: an electric conductivity meter for detecting the electric conductivity of the dilution formed by adding pure water into etching solution in a blending tank or an absorption spectrophotometer for detecting the nitric acid concentration of the etching solution, an absorption spectrophotometer for detecting the moisture concentration of the etching solution, an absorption spectrophotometer or a densitometer for detecting the phosphoric acid concentration of the nitric acid, a component concentration operation mechanism for operating the component concentration of the etching solution by multi-component operation method according to the electric conductivity value of the nitric acid concentration conductivity meter, the absorbency value of the moisture concentration absorption spectrophotometer, and the absorbency value of the phosphoric acid concentration absorption spectrophotometer or the density value of the densitometer, and a replenishing mechanism for replenishing at least one of acid original solution, mixed acid original solution and pure water into the blending tank.
Description
Technical field
The present invention relates in semiconductor manufacturing process or flat-panel monitor manufacturing process (crystal liquid substrate manufacturing process, OLED display manufacturing process etc.), utilize pipeline and aluminium film (second film of the first film of the film of aluminum or aluminum alloy, molybdenum or molybdenum alloy and aluminum or aluminum alloy for example, below, be called the aluminium film) concoct device with the etching solution of Etaching device connection.
Background technology
In the etching work procedure of the aluminium film in crystal liquid substrate manufacturing process etc., as etching solution, the mixed aqueous solution of the mixed aqueous solution of the mixed aqueous solution of nitric acid and phosphoric acid, nitric acid and phosphoric acid and acetic acid, nitric acid and phosphoric acid and malonic acid etc. are that the nitration mixture aqueous solution of principal component waits with sputter mode or impregnation method and uses with acid.Use the mixed aqueous solution of nitric acid and phosphoric acid and acetic acid mostly.For example, can enumerate phosphoric acid concentration is 70.0%, and acetate concentration is 10.0%, and concentration of nitric acid is 4.0%, and remaining moisture concentration is 16.0% the aqueous solution.
The aluminium film of crystal liquid substrate manufacturing process with etching solution for corresponding to etching work procedure, coning angle, stability and the high finished product rate of meticulous, the regulation that obtains that the highest exploring power, pattern forms, have to its composition of strict control and concentration.Especially, the height of following pattern in recent years to form becomes more meticulous, and requires pattern to form the miniaturization of width gradually.To this, also strong request the raising of blending precision of etchant concentration.
In addition, the use amount of etching solution is owing to the maximization of LCD, maximization, the batch processization of the caused glass substrate of employing multiaspect, and etching solution that need be a large amount of.And then because the low-price competition of international LCD, just the cost at the strong request etching solution reduces.
In order to tackle such problem, for example, a plurality of etching baths have been proposed to switch successively, the soup monitor apparatus (for example, with reference to patent documentation 1) that manages with a concentration of measuring system's METHOD FOR CONTINUOUS DETERMINATION soup or temperature.
[patent documentation 1] TOHKEMY 2003-086565 communique.
But in the past, in manufacturing works such as LCD, the situation of using etching solution to the basis of desired value in blending and with concentration adjustment was not only aspect slave unit and the operating cost, and from technological standpoints such as concentration determinations, also extremely difficult.For whether the etching solution of the stoste of the stoste of verifying the stoste of having mixed nitric acid, phosphoric acid, acetic acid and pure water becomes the composition and the concentration of regulation, need to measure the concentration of each composition.
Yet, can not be with the embedded or online concentration of correctly measuring nitric acid, phosphoric acid and the acetic acid of etching solution, the acid concentration after can not the The real time measure blending.
In the past, do not know to be used for the good determination method of three kinds of quantitatively so respectively mixed acid.In etching solution producer, for example, the etching solution after the blending is once sampled, measure acid concentration with the ion chromatography instrument of off line, replenish stoste in shortage and the secondary regulated is concocted.In the part, utilize on-waterborne and titration to measure off and on therein, concoct the device of concentration in batches, but since device complicated, need to use the titration reagent, produce waste liquid, intermittently measure, therefore, produce a large amount of problems such as controlled bad grade.
Thereby, in manufacturing works such as LCD (below, be called " use side "), have to use by etching solution producer (below, be called " supply side ") and regulated the etching solution of composition and concentration.
In this case, mixing is adjusted to the stoste of the nitric acid of normal concentration, the stoste of phosphoric acid, the stoste and the pure water of acetic acid, the etching solution of its composition that becomes regulation and concentration ground blending is filled in the container, to the method for using side to supply with in the supply side employing.
At the etching solution of supply side modulation till using side to use, need be with transportation and keeping corresponding during, in the problem that has during this period the etching solution deterioration.And then the acetic acid in the etching solution has volatility, therefore, exists acetate concentration to reduce, and nitric acid is as NO
xGaseous volatilization, the problem that causes concentration of nitric acid to reduce.
In addition, the etching solution blending device of concocting mode is continuously not only using side not have, and does not also have at supply side.This is because there is not the concentration measurement apparatus of the constituent concentration of METHOD FOR CONTINUOUS DETERMINATION etching solution.These problems also can be used as the blending of etching solution and enumerate the big reason of not carrying out in manufacturing works such as LCD (use side).
Summary of the invention
The present invention In view of the foregoing makes, its purpose is to be provided at the use side, can be by the etching solution of etching stoste precision blending expectation well and promptly concentration, and, the composition of etching solution that can precision administrative institute's blending well and the etching solution blending device of concentration.
In order to realize described purpose, at first, confirmed by experiment the blending groove etching solution concentration of nitric acid and be the fact that has dependency relation between the conductivity of liquid of regulation multiplying power as illustrated in fig. 9 with etching solution with the pure water dilution.In addition, confirmed that by experiment the concentration of nitric acid of the etching solution of blending groove has the situation of dependency relation as illustrated in fig. 10 with its absorbance.In addition, confirmed that by experiment the moisture concentration of the etching solution of blending groove has the situation of dependency relation as illustrated in fig. 11 with its absorbance.And then, confirmed that by experiment the phosphoric acid concentration of etching solution has the situation of dependency relation as illustrated in fig. 12 with its absorbance.In addition, confirmed that by experiment the phosphoric acid concentration of etching solution has the situation of dependency relation as illustrated in fig. 13 with its density.
In the present invention, utilize the conductance measurement of dilute aqueous solution to adjust, control concentration of nitric acid, or utilize absorbance measurement adjustment, control concentration of nitric acid, utilize absorbance measurement adjustment, control moisture concentration, utilize absorbance measurement adjustment, control phosphoric acid concentration, or utilize density measurement adjustment, control phosphoric acid concentration, comprehensively adjust and control this ternary concentration of concentration of nitric acid, moisture concentration and phosphoric acid concentration.
In addition, in the present invention, seek raising based on the concentration operational precision of dependency relation, conductivity value (or absorbance of the extinction photometer of etching solution) according to the conductivity meter of the conductivity that detects the dilution that forms with the etching solution in the pure water dilution blending groove, the absorbance (or densitometric density value) of the extinction photometer of the phosphoric acid concentration of the absorbance of the extinction photometer of the moisture concentration of detection etching solution and detection etching solution, utilize multicomponent operation method (multiple regression analysis method, the multivariable analytic method), the constituent concentration of the etching solution that computing is correct is adjusted, control.In this case, can calculate acetate concentration by deducting concentration of nitric acid, moisture concentration and phosphoric acid concentration from 100%.
That is, to achieve these goals, as Fig. 1 and shown in Figure 5, etching solution blending device of the present invention possesses: the blending aluminium film blending groove of etching solution; The pipeline that is connected with described blending groove; Carry the pump of the liquid that uses in the blending of described etching solution or described etching solution to described pipeline, described etching solution blending device is connected with Etaching device by described pipeline, it is characterized in that, described etching solution blending device possesses: concentration of nitric acid detects, liquid supply establishment, it is based on by utilizing conductivity meter to detect the concentration of nitric acid that dilutes the described etching solution that the conductivity of the dilution that the etching solution in the described blending groove forms obtains with pure water, or the concentration of nitric acid of the described etching solution that obtains by the absorbance of utilizing extinction photometer to detect described etching solution, to the single sour stoste of described blending groove supply, nitration mixture stoste or pure water at least a; Moisture concentration detects, liquid supply establishment, and it is based on by utilizing extinction photometer to detect the moisture concentration of the described etching solution that described etching solution obtains, at least a to the single sour stoste of described blending groove supply, nitration mixture stoste or pure water; Phosphoric acid concentration detects, liquid supply establishment, the phosphoric acid concentration of the described etching solution that it obtains based on the phosphoric acid concentration of the described etching solution that obtains by the absorbance of utilizing extinction photometer to detect described etching solution or by the density of utilizing densitometer to detect described etching solution, at least a to the single sour stoste of described blending groove supply, nitration mixture stoste or pure water.
In addition, as Fig. 2 and shown in Figure 6, etching solution blending device of the present invention possesses: the blending aluminium film blending groove of etching solution; The pipeline that is connected with described blending groove; Carry the pump of the liquid that uses in the blending of described etching solution or described etching solution to described pipeline, described etching solution blending device is connected with Etaching device by described pipeline, it is characterized in that described etching solution blending device possesses: detect with pure water and dilute the etching solution in the described blending groove and the conductivity meter of the conductivity of the dilution that forms or detect the extinction photometer of the concentration of nitric acid of described etching solution; Detect the extinction photometer of the moisture concentration of described etching solution; Detect the extinction photometer or the densitometer of the phosphoric acid concentration of described etching solution; The constituent concentration arithmetical organ, its according to the conductivity value of the described conductivity meter that detects concentration of nitric acid or detect the described extinction photometer of concentration of nitric acid absorbance, detect moisture concentration described extinction photometer absorbance and detect phosphoric acid concentration described extinction photometer absorbance or detect the described densitometric density value of phosphoric acid concentration, utilize multicomponent operation method (multiple regression analysis method, multivariable analytic method) to come the constituent concentration of the described etching solution of computing; Liquid supply establishment, its single sour stoste of supply, nitration mixture stoste and pure water at least a in described blending groove.
In addition, etching solution blending device of the present invention is characterised in that, described etching solution is the aqueous solution that contains phosphoric acid, nitric acid, described etching solution is at least a aqueous solution that also contains organic acid, hydrochloric acid, sulfuric acid, perchloric acid, described organic acid is acetic acid, malonic acid, and described etching solution blending device adopts continuous blending mode.
The invention effect
As mentioned above, according to etching solution blending device of the present invention, play following effect.
(1), can realize being difficult to the etching solution blending device of the aluminium that carries out in the use side of semiconductor fabrication factory or flat-panel monitor manufacturing works in the past.
(2) concentration of nitric acid, moisture concentration, phosphoric acid concentration and the acetate concentration of can real-time continuous measuring etching solution, can be constant and precision well continuously blending be normal concentration.
(3) acetic acid in etching solution has volatility so acetate concentration reduction, and nitric acid is as NO
xGaseous volatilization, under the situation that concentration of nitric acid reduces, also therefore METHOD FOR CONTINUOUS DETERMINATION concentration, be adjusted into the concentration of desired value automatically.
(4) precision of the concentration of Tiao He etching solution is good and constant, therefore, the control stabilizationization of the high fine size of aluminium film, in addition, the control of the coning angle of aluminium film is stabilisation also, and the rate of finished products of product increases substantially.
(5) using side, can carry out the blending of etching solution and the checking of concentration, therefore, can realize that the manufacturing of a large amount of etching solutions, usefulness pipeline reduce to the direct supply and the cost of Etaching device.
Description of drawings
Fig. 1 is the system diagram of the etching solution blending device of first execution mode of the present invention.
Fig. 2 is the system diagram of the etching solution blending device of second execution mode of the present invention.
Fig. 3 is the system diagram of the etching solution blending device of the 3rd execution mode of the present invention.
Fig. 4 is the system diagram of the etching solution blending device of the 4th execution mode of the present invention.
Fig. 5 is the system diagram of the etching solution blending device of the 5th execution mode of the present invention.
Fig. 6 is the system diagram of the etching solution blending device of the 6th execution mode of the present invention.
Fig. 7 is the system diagram of the etching solution blending device of the 7th execution mode of the present invention.
Fig. 8 is the system diagram of the etching solution blending device of the 8th execution mode of the present invention.
Fig. 9 is the chart of relation of the conductivity of expression concentration of nitric acid of etching solution of the present invention and dilution.
Figure 10 is the chart of the relation of expression concentration of nitric acid of etching solution of the present invention and absorbance.
Figure 11 is the chart of the relation of expression moisture concentration of etching solution of the present invention and absorbance.
Figure 12 is the chart of the relation of expression phosphoric acid concentration of etching solution of the present invention and absorbance.
Figure 13 is the chart of the relation of expression phosphoric acid concentration of etching solution of the present invention and density.
Among the figure: 1-concocts groove; 2-liquid level instrument; The 3-pump of sampling; The 4-force cell; The 11-circulating pump; The 15-conductivity meter; The 16-extinction photometer; 17-extinction photometer (densitometer); The 19-extinction photometer; 20-phosphoric acid stoste supplying tank; 21-acetic acid stoste supplying tank; 22-nitric acid stoste supplying tank; 24-phosphagen flow quantity adjuster valve; 25-acetic acid stoste adjuster valve; 26-nitric acid stock solution flow adjuster valve; 27-pure water flow control valve; 30-conductivity controller; 31-absorbance controller; 32-absorbance controller (density controller); 33-multicomponent arithmetic unit; 40-absorbance controller.
Embodiment
Below, the execution mode that is fit to that present invention will be described in detail with reference to the accompanying.Wherein, the shape of the structural device of putting down in writing in these execution modes, its corresponding configuration etc. is not having under the situation of special specific record, and the present invention not only is defined in these, only is illustrative examples.
Fig. 1 is the plant system drawing of expression first execution mode of the present invention.Reference marks among the figure is equipment and the parts that constitute etching solution blending device.That is, this etching solution blending device comprises: the blending groove 1 of blending etching solution, liquid level instrument 2, the circulating pump that cleans and stir 11 (also carrying out simultaneously carrying) that is used for etching solution to Etaching device, pipeline 12, be used for removing the filter 13 of the minuteness particle etc. of etching solution, circulation is stirred with air valve 14, phosphoric acid stoste supplying tank 20, phosphoric acid stoste is supplied with flow control valve 24, acetic acid stoste supplying tank 21, acetic acid stoste is supplied with flow control valve 25, nitric acid stoste supplying tank 22, nitric acid stoste is supplied with flow control valve 26, pure water is supplied with flow control valve 27, to the conveying liquid that uses point (use point) air valve 29, the pipe arrangement class and the N that connect these each equipment
2Pipe arrangement classes such as gas pipe arrangement 23, pure water etc.
Based on the present invention, the equipment that is attached to above-mentioned etching solution blending device is for sampling pump 3, dilution pumps 38, pure water pump 39, the conductivity meter 15 that detects concentration of nitric acid, the extinction photometer 16 that detects moisture concentration, the extinction photometer 17 that detects phosphoric acid concentration, electric instrument is installed by class or the air instrument is installed class etc.
Supplying with liquid is phosphoric acid stoste, acetic acid stoste, nitric acid stoste, nitration mixture stoste and pure water, but may not necessarily need all, according to the acquisition condition of the composition of etching solution, appointed condition, service conditions, supply liquid etc., select best supply liquid and feedway, also identical for Fig. 2～Fig. 8.
As the blending mode, preferred blending mode continuously, but also can be for concoct mode in batches.Under the situation of continuous blending mode, once using pure water, phosphoric acid stoste, acetic acid stoste, nitric acid stoste in the blending, form a blending liquid that is rich in acetic acid that has increased acetate concentration, also can utilize replenishing of pure water, phosphoric acid stoste, nitric acid stoste, finely tune and be normal concentration.Under the situation of in batches concocting mode, the blending of stoste order is good by pure water, phosphoric acid stoste, acetic acid stoste, nitric acid stoste.
The phosphoric acid stoste supplying tank 20 of storing phosphoric acid stoste is by the N from pipe arrangement 23
2Gas is pressurised into 0.1～0.2MPa, opens force feed by phosphagen flow quantity adjuster valve 24.The acetic acid stoste supplying tank 21 of storing acetic acid stoste is by the N from pipe arrangement 23
2Gas is pressurised into 0.1～0.2MPa, opens force feed by acetic acid stock solution flow adjuster valve 25.The nitric acid stoste supplying tank 22 of storing nitric acid stoste is by the N from pipe arrangement 23
2Gas is pressurised into 0.1～0.2MPa, opens force feed by nitric acid stock solution flow adjuster valve 26.Pure water communicates with the manifold that comes own establishing pipe, carries by pure water flow control valve 27.These supply with liquid is to carry by automatic adjusting valve separately, is supplied in blending groove 1.
In addition, the sampling pump 3 that utilizes pipeline 18 is from 1 sampling of blending groove, utilize the dilution pumps of pipeline 34 to get in 38 minutes the part of the etching solution of described sampling, make the pure water interflow from pure water pump 39 of itself and pipeline 35, and utilize pipeline 36 to mix stirring, dilute for behind the requirement ratio, in the conductivity meter 15 that detects concentration of nitric acid, the conductivity of METHOD FOR CONTINUOUS DETERMINATION dilution is discharged the dilution of having measured from pipeline 37.
The preferred serial dilution mode of the dilution mode of utilizing pure water of etching solution, but also can be for accept the dilution mode in batches of etching solution and pure water at tank diameter etc.
By measuring the conductivity of dilution, can measure the concentration of nitric acid of dilution, but dilution is requirement ratio (for example 10 times), therefore, can measure the concentration of nitric acid of the preceding etching solution of dilution.Also have, the conductivity of the etching solution before measuring dilution, when measuring concentration of nitric acid, phosphoric acid concentration or acetate concentration are big to the influence of conductivity, thereby are difficult to carry out.
Fig. 2 is the plant system drawing of expression second execution mode of the present invention.In the present embodiment, in first execution mode, added the multicomponent arithmetic unit 33 that is used to improve the mensuration precision.Other structures etc. are identical with the situation of Fig. 1.
Fig. 3 is the plant system drawing of expression the 3rd execution mode of the present invention.In the present embodiment, utilize sampling pump 3 from 1 sampling of blending groove, import sample liquids from pipeline 18 to the extinction photometer 17 of the extinction photometer 19 of the detection concentration of nitric acid of online setting, the extinction photometer 16 that detects moisture concentration and detection phosphoric acid concentration, the METHOD FOR CONTINUOUS DETERMINATION absorbance, and make the liquid of having measured return blending groove 1.Other structures etc. are identical with the situation of Fig. 1.
Fig. 4 is the plant system drawing of expression the 4th execution mode of the present invention.In the present embodiment, in the 3rd execution mode, added the multicomponent arithmetic unit 33 that is used to improve the mensuration precision.Other structures etc. are identical with the situation of Fig. 1.
Fig. 5 is the plant system drawing of expression the 5th execution mode of the present invention.In the present embodiment, in order concoct in batches, to replace liquid level instrument 2, at the blending groove 1 of Fig. 1 force cell 4 to be installed, correctly measure the weight of the blending liquid of blending groove 1, the control of once concocting reaches the concentration adjustment based on the concentration determination value.Other structures etc. are identical with the situation of Fig. 1.
Fig. 6 is the plant system drawing of expression the 6th execution mode of the present invention.In the present embodiment, in order to concoct in batches, replace liquid level instrument 2, at the blending groove 1 of Fig. 2 force cell 4 has been installed, correctly measure the weight of the blending liquid of blending groove 1, carry out control according to the additional Weight Calculation and the additional weight of concentration determination value.Other structures etc. are identical with the situation of Fig. 2.
Fig. 7 is the plant system drawing of expression the 7th execution mode of the present invention.In the present embodiment, in order concoct in batches, to replace liquid level instrument 2, at the blending groove 1 of Fig. 3 force cell 4 to be installed, correctly measure the weight of the blending liquid of blending groove 1, the control of once concocting reaches the concentration adjustment based on the concentration determination value.Other structures etc. are identical with the situation of Fig. 3.
Fig. 8 is the plant system drawing of expression the 6th execution mode of the present invention.In the present embodiment, in order to concoct in batches, in the blending groove 1 of Fig. 4, replace liquid level instrument 2, force cell 4 has been installed, has correctly been measured the weight of the blending liquid of blending groove 1, carried out control by the additional Weight Calculation and the additional weight of concentration determination value.Other structures etc. are identical with the situation of Fig. 4.
Secondly, the control system of the device of the execution mode of key diagram 1～shown in Figure 8.In Fig. 1～4, liquid level instrument 2 and the independent respectively basically function of bringing into play of the phosphoric acid concentration of moisture concentration, extinction photometer 17 (or densitometer 17) and the etching solution of concentration of nitric acid, extinction photometer 16 and the etching solution of liquid level face, conductivity meter 15 (or extinction photometer 19) and the etching solution of blending groove 1, but in the present invention, it is characterized in that, make it in the association of mutual completion, bring into play function.With regard to the concentration of etching solution, in order to carry out etching,, need manage concentration into regulation based on the etching of the etching side of the best based on the etching speed of the best.In addition, at first the desired value of the desired value of the desired value of the desired value of the concentration of nitric acid of required etching solution, moisture concentration, phosphoric acid concentration, acetate concentration etc. need be pre-set in each controller based on operation actual achievement or calculating in the quality management of product substrate.
Below, to as etching solution, use the embodiment of the solution that has mixed nitric acid, phosphoric acid, acetic acid and pure water to describe.
To the concentration of nitric acid of etching solution,, need manage concentration range into regulation in order to bring into play best etching performance.Concentration of nitric acid needs to concoct the desired value into regulation sometimes, and for example 4.0 ± 0.5%.
The inventor inquired into the concentration of nitric acid of etching solution and the relation of conductivity by experiment, confirmed by experiment the blending groove etching solution concentration of nitric acid and be the situation that has dependency relation between the conductivity of liquid of regulation multiplying power with pure water with the etching solution dilution.As shown in Figure 9, having confirmed with pure water to be that the conductivity of liquid of regulation multiplying power and the concentration of nitric acid of etching solution are linear relation with etching solution dilution, is the conductivity of the liquid of regulation multiplying power by detecting with pure water with the etching solution dilution, can measure concentration of nitric acid.Shown in Fig. 1,5, the conductivity meter 15 that is provided with at pipeline 37 possesses: be used for evaluated error is made as minimal each compensate function and conductivity controller 30.To be that the conductance measurement value of the liquid of regulation multiplying power is input into conductivity controller 30 with pure water dilution, according to output signal, utilize flow control valve 24,25,26,27 control phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water at least a automatically respectively, till being replenished to concentration of nitric acid with becoming desired value and being adjusted into desired value with its value.
The inventor inquired into the concentration of nitric acid of etching solution and the relation of absorbance by experiment, by experiment, confirmed the blending groove etching solution concentration of nitric acid and the absorbance of etching solution between have the situation of dependency relation.The scope of the 250nm～320nm of preferred ultraviolet range in the mensuration wavelength of absorbance, near the sensitivity the 290nm is big, especially preferred.As shown in figure 10, the absorbance and the concentration of nitric acid that confirm the ultraviolet extinction photometer among mensuration wavelength X=290nm have the linear relation of height, can correctly measure the situation of concentration of nitric acid by measuring absorbance.Shown in Fig. 3,7, possess at the extinction photometer 19 of pipeline 18 online settings and to be used to make evaluated error to become the absorbance controller 40 of minimal each compensate function of performance.The absorbance measurement value of the sample liquid that will import from pipeline 18 is input into absorbance controller 40, according to output signal, utilize flow control valve 24,25,26,27 control phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water at least a automatically respectively, till being replenished to concentration of nitric acid with becoming desired value and being adjusted into desired value with its value.
In addition, the moisture concentration of etching solution need be managed the concentration range into regulation in order to bring into play best etching performance.Therefore, moisture concentration need be concocted the desired value that is regulation, and for example 16.0 ± 1.0%.
The inventor inquired into the moisture concentration of etching solution and the relation of absorbance by experiment, by experiment, confirmed the blending groove etching solution moisture concentration and the absorbance of etching solution between have the situation of dependency relation.The scope of the 1920nm～1960nm of preferred near infrared range in the mensuration wavelength of absorbance, near the sensitivity the 1931nm is big, especially preferred.As shown in figure 11, the absorbance and the moisture concentration that confirm among mensuration wavelength X=1931nm have the linear relation of height, can correctly measure the situation of moisture concentration by measuring absorbance.Shown in Fig. 1,3,5,7, possess at the extinction photometer 16 of pipeline 18 online settings and to be used to make evaluated error to become the absorbance controller 31 of minimal each compensate function of performance.The absorbance measurement value of the sample liquid that will import from pipeline 18 is input into absorbance controller 31, according to output signal, utilize flow control valve 24,25,26,27 control phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water at least a automatically respectively, till being replenished to moisture concentration with becoming desired value and becoming desired value with its value.
In addition, to the phosphoric acid concentration of etching solution,, need manage concentration range into regulation in order to bring into play best etching performance.Therefore, phosphoric acid concentration need be concocted the desired value that is regulation, and for example 70.0 ± 1.0%.
The inventor has inquired into the phosphoric acid concentration of etching solution and the relation of absorbance by experiment, the scope of the 2050nm～2200nm of preferred near infrared range in the mensuration wavelength of absorbance, and near the sensitivity the 2101nm is big, especially preferred.As shown in figure 12, the absorbance and the phosphoric acid concentration that confirm among mensuration wavelength X=2101nm have linear relation, can measure the situation of moisture concentration by measuring absorbance.Shown in Fig. 1,3,5,7, possess at the extinction photometer 17 of pipeline 18 online settings: be used to make evaluated error to become the absorbance controller 32 of minimal each compensate function of performance.The absorbance measurement value input absorbance controller 32 of the sample liquid that will import from pipeline 18, according to output signal, utilize flow control valve 24,25,26,27 control phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water at least a automatically respectively, till being replenished to phosphoric acid concentration with becoming desired value and being adjusted into desired value with its value.
In addition, the inventor has inquired into the phosphoric acid concentration of etching solution and the relation of density by experiment, finds the rising based on phosphoric acid concentration, the situation that density uprises.As shown in figure 13, confirm density and phosphoric acid concentration has linear relation, can measure phosphoric acid concentration by measuring density.In Fig. 1,3,5,7, extinction photometer 17 is replaced into densitometer, absorbance controller 32 is replaced into density controller, for function association, identical with the situation of extinction photometer 17 and absorbance controller 32.
And then, the inventor is by research and parsing based on dependency relation, as described later shown in the table 1, can be according to the conductivity value of the conductivity meter of the conductivity of measuring the dilution that forms with the etching solution in the pure water dilution blending groove (or measure the concentration of nitric acid of etching solution absorbance of extinction photometer), this three specific characters value of absorbance (or densitometric density value) of the extinction photometer of the phosphoric acid concentration of the absorbance of the extinction photometer of the moisture concentration of mensuration etching solution and mensuration etching solution, utilize linear multiple regression analysis method (MLR-ILS), computing is also obtained the constituent concentration of correct etching solution.In this case, by deducting concentration of nitric acid, moisture concentration and phosphoric acid concentration from 100%, can calculate acetate concentration.
As shown in Figure 2, the output of the measured value of self-conductance rate meter 15, extinction photometer 16 and extinction photometer 17 in the future is input into multicomponent arithmetic unit 33, utilize multicomponent operation method (multiple regression analysis method, multivariable analytic method), the constituent concentration of the etching solution that computing is correct is adjusted, is controlled.For making concentration of nitric acid, acetate concentration, moisture concentration and phosphoric acid concentration become desired value, output signal according to multicomponent arithmetic unit 33, utilize flow control valve 24,25,26,27 to control at least a of phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water respectively automatically, be replenished to each constituent concentration and be adjusted into desired value.The explanation of Fig. 4, Fig. 6, Fig. 8 is also identical with the explanation of Fig. 2, therefore omits.
In the execution mode of Fig. 1～Fig. 4, also can adopt blending mode in batches to use, adopt continuous blending mode to use at this.At this, narrate the function association of the control system that the device of first execution mode shown in Figure 1 realizes.Liquid level instrument 2 is connected with not shown liquid level controller.At blending groove 1 for empty when building bath (building bath), detecting liquid level instrument 2 is empty situation, output signal according to the liquid level controller, utilize flow control valve 24,25,26,27 control phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water and conveying automatically respectively, the liquid level face is located at desired location.In blending once, use pure water, phosphoric acid stoste, acetic acid stoste, nitric acid stoste to form an acetate concentration blending liquid being rich in acetic acid bigger than the new liquid of etching, finely tune concentration by phosphoric acid stoste, nitric acid stoste, supplementary pure water into regulation.Also have, also can be with output signal according to the liquid level controller, make phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water become mode with the new liquid of etching concentration about equally,, utilize flow control valve 24,25,26,27 control valve openings and carry with suitable flow-rate ratio.
Then, the conductivity of the dilution of conductivity meter 15 METHOD FOR CONTINUOUS DETERMINATION etching solutions, output signal according to conductivity controller 30, utilize at least one control valve opening of flow control valve 24,25,26 and 27, the at least a of phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water carried with suitable tiny flow quantity, and the concentration of nitric acid ground that becomes desired value is controlled automatically.
Under the little situation of concentration of nitric acid, the conductivity of the dilution of conductivity meter 15 METHOD FOR CONTINUOUS DETERMINATION etching solutions, output signal according to conductivity controller 30, utilize flow control valve 26 control valve openings, nitric acid stoste is carried with suitable tiny flow quantity, and the concentration of nitric acid ground that becomes desired value is controlled automatically.In addition, the moisture concentration of extinction photometer 16 METHOD FOR CONTINUOUS DETERMINATION etching solutions, output signal according to absorbance controller 31, utilize at least one control valve opening of flow control valve 24,25,26 and 27, the at least a of phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water carried with suitable tiny flow quantity, and the concentration of nitric acid ground that becomes desired value is controlled automatically.
Under the little situation of moisture concentration, the moisture concentration of extinction photometer 16 METHOD FOR CONTINUOUS DETERMINATION etching solutions according to the output signal of absorbance controller 31, utilizes flow control valve 27 control valve openings, pure water is carried with suitable tiny flow quantity, for the moisture concentration that becomes desired value is controlled automatically.
In addition, the phosphoric acid concentration of extinction photometer 17 METHOD FOR CONTINUOUS DETERMINATION etching solutions, output signal according to absorbance controller 32, utilize at least one control valve opening of flow control valve 24,25,26 and 27, the at least a of phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water carried with suitable tiny flow quantity, and the concentration of nitric acid ground that becomes desired value is controlled automatically.
Under the little situation of phosphoric acid concentration, the phosphoric acid concentration of extinction photometer 17 METHOD FOR CONTINUOUS DETERMINATION etching solutions, output signal according to absorbance controller 32, utilize flow control valve 24 control valve openings, phosphoric acid stoste is carried with suitable tiny flow quantity, and the phosphoric acid concentration ground that becomes desired value is controlled automatically.
Secondly, the function association of the control system that the device of second execution mode shown in Figure 2 is realized is narrated.Present embodiment mainly is applicable in situation of correctly measuring concentration of nitric acid, moisture concentration, phosphoric acid concentration and acetate concentration and concocting etc.As shown in Figure 2, output from the measured value of conductivity meter 15, extinction photometer 16 and extinction photometer 17 inputs in the multicomponent arithmetic unit 33, utilize multicomponent operation method (multiple regression analysis method, multivariable analytic method), the constituent concentration of the etching solution that computing is correct is adjusted, is controlled.At blending groove 1 for empty when building bath, detecting liquid level instrument 2 is empty situation, output signal according to the liquid level controller, utilize flow control valve 24,25,26,27 control automatically respectively, carry phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water, the liquid level face is located at desired location.In once concocting, utilize flow control valve 24,25,26,27 control valve openings, for being become with the new liquid of etching concentration about equally, phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water carry with suitable flow-rate ratio.Then, make concentration of nitric acid, acetate concentration, moisture concentration and phosphoric acid concentration become the output signal of desired value ground according to multicomponent arithmetic unit 33, utilize flow control valve 24,25,26,27 control phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water and conveying automatically respectively, be replenished to each constituent concentration and be adjusted into till the desired value.According to from the signal that requires that uses point, move circulation and carry liquor pump 11, open and carry liquid to carry liquid to the use point with air valve 29.If begin to carry liquid, then the liquid level face reduces, therefore, detect the situation that liquid level instrument 2 reduces, output signal according to the liquid level controller, utilize flow control valve 24,25,26,27 control phosphoric acid stoste, acetic acid stoste, nitric acid stoste and pure water and conveying automatically respectively, make the liquid level face return to desired location.For the function association of other control system, identical with the situation of Fig. 1.
[multicomponent arithmetic unit 33]
The inventor found through experiments under the situation of nitric acid, phosphoric acid and acetic acid coexistence, the measured value of the density of the absorbance of the conductivity of the dilute aqueous solution of concentration of nitric acid, the absorbance of concentration of nitric acid, moisture concentration, the absorbance of phosphoric acid concentration, phosphoric acid concentration is not respectively only to a composition induction, but it is interrelated, therefore, if do not utilize multiple regression analysis then can not ask correct concentration.
In addition, the inventor has carried out found that based on the research of dependency relation and parsing, can (measure the absorbance of extinction photometer of the concentration of nitric acid of the conductivity value of conductivity meter of conductivity of the dilution that forms with the etching solution in the etch processes groove with pure water dilution aluminium film or mensuration etching solution according to three specific character values, the absorbance of the extinction photometer of the moisture concentration of mensuration etching solution, the absorbance (or densitometric density value) of the extinction photometer of the phosphoric acid concentration of mensuration etching solution), utilize the constituent concentration (concentration of nitric acid of linear multiple regression analysis method (MLR-ILS) etching solution that further computing is correct, moisture concentration and phosphoric acid concentration), by deducting the concentration of nitric acid that this calculates from 100%, moisture concentration and phosphoric acid concentration are calculated acetate concentration.
At this, the arithmetic expression of illustration multiple regression analysis.Multiple regression analysis comprises correction and predicts this two stages.In the multiple regression analysis of n composition system, prepared m and revised standard liquid.The concentration of j composition existing in i the solution is expressed as C
IjAt this, i=1～m, j=1～n.At m standard liquid, measure p characteristic value (for example absorbance or the conductivity under certain wavelength) A respectively
Ik(k=1～p).Concentration data and characteristic value data respectively can conclusive table be shown matrix form (C, A).
[formula 1]
The matrix of these matrix opening relationships is called correction matrix, at this, with symbol S (S
KjK=1～p, j=1～n).
[formula 2]
C＝A·S
(not only be mixed with the measured value of same nature in the content of A, can also be mixed with measured value of different nature according to known C and A.For example, absorbance and conductivity), the situation of utilizing matrix operation to calculate S is the correction stage.At this moment, need satisfy p 〉=n, and m 〉=np.Each key element of S is unknown number, and therefore, preferred m＞np in this case, carries out the least square method computing as described below.
[formula 3]
S＝(A
T?A)
-1(A
T?C)
At this, last target T represents transposed matrix, last target-1 expression inverse matrix.At the sample liquid of concentration the unknown, measure p characteristic value, these are made as Au (Auk; Under the situation of k=1～p), can access S is taken advantage of the concentration C u (Cuj that obtains in it; J=1～n).
[formula 4]
Cu＝Au·S
This is a forecast period.To revise one of standard 12 (revising standard liquid for 12) and be chosen as unknown test portion, obtain correction matrix with residue 11 standards, calculate the concentration of the unknown test portion of hypothesis, utilize the method for comparing with known value (weight modulation value) to stay a proof method (Leave-One-out), the result of calculation of having carried out MLR-ILS calculating is shown in the table 1.Table 1 is the concentration of the phosphoric acid obtained by near-infrared 2 wavelength (1931,2101nm) and 10 times of dilution conductivity, nitric acid, moisture.
[table 1]
Multicomponent arithmetic unit 33 utilizes multicomponent operation method (multiple regression analysis method, multivariable analytic method) based on foregoing invention people's opinion, and the constituent concentration of the etching solution that computing is correct is adjusted, controlled.
Connect conductivity meter 15, extinction photometer 16 and extinction photometer 17 at multicomponent arithmetic unit 33.
Multicomponent arithmetic unit 33 bases are from conductivity meter 15, the conductivity of extinction photometer 16 and extinction photometer 17 inputs, each absorbance, utilize multicomponent operation method (multiple regression analysis fado variable analytic method), constituent concentration (the concentration of nitric acid of the etching solution that computing is more correct, moisture concentration and phosphoric acid concentration), and then, from 100% concentration of nitric acid that deducts this computing, moisture concentration and phosphoric acid concentration, and calculate acetate concentration, the desired value ground that these each concentration is become predesignate is to flow control valve 24,25,26, at least one flow control valve in 27 carries out open and close controlling.Thus, will be supplied in the etch processes groove 1, adjust each constituent concentration corresponding to the stoste or the pure water of the flow control valve of described control.
Secondly, the function association of the control system that the device of the 3rd execution mode shown in Figure 3 is realized is narrated.In the present embodiment, replace utilizing conductivity meter to detect the conductivity of the dilution that forms with the etching solution in the blending groove of pure water dilution Fig. 1, utilize extinction photometer to detect the concentration of nitric acid of described etching solution and control.The function association of other control system is identical with the situation of Fig. 1.
Secondly, the function association of the control system that the device of the 4th execution mode shown in Figure 4 is realized is narrated.In the present embodiment, replace utilizing conductivity meter to detect the conductivity of the dilution that forms with the etching solution in the blending groove of pure water dilution Fig. 2, utilize extinction photometer to detect the concentration of nitric acid of described etching solution and control.The function association of other control system is identical with the situation of Fig. 2.
In continuous blending mode, usually, the liquid level face of blending groove is controlled to be to be kept near the upper limit level face of filling.That is, deliver to storagetank or use point, under the situation that the liquid level face reduces, once concoct immediately, then, make each constituent concentration become desired value ground and adjust control at the etching solution of being concocted.Thereby the liquid level face of blending groove is kept the state of filling, and therefore, also has the function as effective storagetank simultaneously.
The execution mode of Fig. 5～Fig. 8 uses in blending mode in batches.At this, the function association of the control system that the device of the 5th execution mode shown in Figure 5 is realized is narrated.In the present embodiment, in order concoct in batches, to replace liquid level instrument 2 and installation force cell 4 on the blending groove 1 of Fig. 1, correctly to measure the weight of the blending liquid of blending groove 1, the control of once concocting reaches the concentration adjustment based on the concentration determination value.The roughly total amount of the etching solution of blending is delivered to storagetank or is used point, and blending groove 1 becomes empty state.At blending groove 1 is under the state of sky, and force cell 4 detects the situation of lower limits, and according to the output signal of force cell 4, the blending weight of utilizing flow control valve 27 to be delivered to pure water becomes till the predetermined weight.
Secondly, according to the output signal of force cell 4, the blending weight of utilizing flow control valve 24 to be delivered to phosphoric acid stoste becomes till the predetermined weight.Then, according to the output signal of force cell 4, the blending weight of utilizing flow control valve 25 to be delivered to acetic acid stoste becomes till the weight of regulation.And then according to the output signal of force cell 4, the blending weight of utilizing flow control valve 26 to be delivered to nitric acid stoste becomes till the weight of regulation.At this, utilize the mixed liquor that mixes in the circulating pump 11 stir-concoction grooves 1.
Secondly, measure each constituent concentration of the mixed liquor that utilizes 3 sampling of sampling pump.According to the blending weight of each stoste and the concentration determination value of each constituent concentration, carry out phosphoric acid stoste, acetic acid stoste, nitric acid stoste, supplementary pure water control, utilize flow control valve 24,25,26,27 control and conveying automatically respectively, make its concentration that becomes desired value ground carry out inching.At this, utilize the mixed liquor that mixes in the circulating pump 11 stir-concoction grooves 1 once more.Then, measure each constituent concentration of the mixed liquor that utilizes 3 sampling of sampling pump.The concentration determination value of each constituent concentration is included under the situation of concentration range of desired value, finishes the blending of 1 batch.Function association for other control system is identical with the situation of Fig. 1.
Secondly, the function association of the control system that the device of the 6th execution mode shown in Figure 6 is realized is narrated.In the present embodiment, in order to concoct in batches, on the blending groove 1 of Fig. 2, replace liquid level instrument 2 and force cell 4 is installed, correctly measure the weight of the blending liquid of blending groove 1, in multicomponent arithmetic unit 33, carry out the control of the correct calculation of concentration determination value, additional Weight Calculation and additional weight.The roughly total amount of the etching solution of blending is delivered to storagetank or uses point, and then concocting groove 1 becomes empty state.At blending groove 1 is that force cell 4 detects the situation of lower limit under the state of sky, and according to the output signal of force cell 4, the blending weight of utilizing flow control valve 27 to be delivered to pure water becomes till the weight of regulation.Then, according to the output signal of force cell 4, the blending weight of utilizing flow control valve 24 to be delivered to phosphoric acid stoste becomes till the weight of regulation.Then, according to the output signal of force cell 4, the blending weight of utilizing flow control valve 25 to be delivered to acetic acid stoste becomes till the weight of regulation.And then according to the output signal of force cell 4, the blending weight of utilizing flow control valve 26 to be delivered to nitric acid stoste becomes till the weight of regulation.At this, utilize the mixed liquor that mixes in the circulating pump 11 stir-concoction grooves 1.Then, measure each constituent concentration of the mixed liquor that utilizes 3 sampling of sampling pump.In multicomponent arithmetic unit 33, according to the control of the blending weight of each stoste and the concentration determination value of each constituent concentration, and utilize phosphoric acid stoste, acetic acid stoste, nitric acid stoste, supplementary pure water Weight Calculation to replenish the control of weight, utilize flow control valve 24,25,26,27 control and conveying automatically respectively, so that its concentration ground that becomes desired value carries out inching.At this, utilize the mixed liquor of the mixing in the circulating pump 11 stir-concoction grooves 1 once more.Then, measure each constituent concentration of the mixed liquor that utilizes 3 sampling of sampling pump.Under the situation in the concentration determination value of each constituent concentration is included in the concentration range of desired value, finish the blending of a batch.The function association of other control system is identical with the situation of Fig. 5.For the function association of the control system of Fig. 7, Fig. 8, also identical with the explanation of Fig. 5, Fig. 6, therefore omit.
The inventor finds, by using with the association of mutual completion based on the result of each controlled function as described above, can realize easily that comprehensive etching solution forms constant blending and blending continuously.
Also have, more than in the narration, the invention is not restricted to as etching solution, used the situation of the solution of nitric acid, acetic acid, phosphoric acid and pure water, can also be applicable to as etching solution, used the solution of phosphoric acid, nitric acid and pure water, comprised at least a aqueous solution of phosphoric acid, nitric acid and organic acid, hydrochloric acid, sulfuric acid, perchloric acid, described organic acid is the situation etc. of the aqueous solution of acetic acid, malonic acid.
Claims (8)
1. an etching solution is concocted device, and it possesses: the blending aluminium film blending groove of etching solution; The pipeline that is connected with described blending groove; Carry the pump of the liquid that uses in the blending of described etching solution or described etching solution to described pipeline, described etching solution blending device is connected with Etaching device by described pipeline, it is characterized in that described etching solution is concocted device and possessed:
Concentration of nitric acid detects, liquid supply establishment, it is based on diluting the concentration of nitric acid of the described etching solution that the conductivity of the dilution that the etching solution in the described blending groove forms obtains or the concentration of nitric acid of the described etching solution that obtains by the absorbance of utilizing extinction photometer to detect described etching solution by utilizing conductivity meter to detect with pure water, at least a to the single sour stoste of described blending groove supply, nitration mixture stoste or pure water;
Moisture concentration detects, liquid supply establishment, and it is based on by utilizing extinction photometer to detect the moisture concentration of the described etching solution that described etching solution obtains, at least a to the single sour stoste of described blending groove supply, nitration mixture stoste or pure water;
Phosphoric acid concentration detects, liquid supply establishment, the phosphoric acid concentration of the described etching solution that it obtains based on the phosphoric acid concentration of the described etching solution that obtains by the absorbance of utilizing extinction photometer to detect described etching solution or by the density of utilizing densitometer to detect described etching solution, at least a to the single sour stoste of described blending groove supply, nitration mixture stoste or pure water.
2. an etching solution is concocted device, and it possesses: the blending aluminium film blending groove of etching solution; The pipeline that is connected with described blending groove; Carry the pump of the liquid that uses in the blending of described etching solution or described etching solution to described pipeline, described etching solution blending device is connected with Etaching device by described pipeline, it is characterized in that described etching solution is concocted device and possessed:
Detection is diluted the etching solution in the described blending groove with pure water and the conductivity meter of the conductivity of the dilution that forms or detect the extinction photometer of the concentration of nitric acid of described etching solution;
Detect the extinction photometer of the moisture concentration of described etching solution;
Detect the extinction photometer or the densitometer of the phosphoric acid concentration of described etching solution;
The constituent concentration arithmetical organ, its according to the conductivity value of the described conductivity meter that detects concentration of nitric acid or detect the described extinction photometer of concentration of nitric acid absorbance, detect moisture concentration described extinction photometer absorbance and detect phosphoric acid concentration described extinction photometer absorbance or detect the described densitometric density value of phosphoric acid concentration, utilize multicomponent operation method (multiple regression analysis method, multivariable analytic method) to come the constituent concentration of the described etching solution of computing;
Liquid supply establishment, its single sour stoste of supply, nitration mixture stoste and pure water at least a in described blending groove.
3. etching solution blending device according to claim 1 and 2, wherein,
Described etching solution is the aqueous solution that contains phosphoric acid, nitric acid.
4. etching solution blending device according to claim 3, wherein,
Described etching solution is at least a aqueous solution that also contains organic acid, hydrochloric acid, sulfuric acid, perchloric acid.
5. etching solution blending device according to claim 4, wherein,
Described organic acid is acetic acid, malonic acid.
6. concoct device according to each described etching solution in the claim 1～5, wherein,
Described etching solution blending device adopts continuous blending mode.
7. etchant concentration determinator is characterized in that possessing:
The conductivity meter of the conductivity of the dilution that detection forms with etching solution with pure water dilution aluminium film or detect the extinction photometer of the concentration of nitric acid of described etching solution;
Detect the extinction photometer of the moisture concentration of described etching solution;
Detect the extinction photometer or the densitometer of the phosphoric acid concentration of described etching solution;
The constituent concentration arithmetical organ, its according to the conductivity value of the described conductivity meter that detects conductivity or detect the described extinction photometer of concentration of nitric acid absorbance, detect moisture concentration described extinction photometer absorbance and detect phosphoric acid concentration described extinction photometer absorbance or detect the described densitometric density value of phosphoric acid concentration, utilize multicomponent operation method (multiple regression analysis method, multivariable analytic method) to come the constituent concentration of the described etching solution of computing.
8. etchant concentration determinator according to claim 7, wherein,
The absorption photometric that detects the concentration of nitric acid of described etching solution is counted the ultraviolet light absorption photometer of the wavelength that has used the ultraviolet range.
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- 2009-04-07 KR KR1020090029960A patent/KR101213108B1/en active IP Right Grant
- 2009-04-14 TW TW098112317A patent/TWI454872B/en not_active IP Right Cessation
- 2009-04-15 CN CN2009101331960A patent/CN101567309B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001201476A (en) * | 2000-01-20 | 2001-07-27 | Sumitomo Metal Ind Ltd | Acid densitometer and method for measuring acid concentration |
| CN1532305A (en) * | 2002-10-15 | 2004-09-29 | 长濑产业株式会社 | Etching liquid managing method and etching liquid managing device |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169102A (en) * | 2011-01-13 | 2011-08-31 | 福州大学 | Method for monitoring and analyzing concentration of nano-carbon material electrophoretic deposition liquid |
| CN102169102B (en) * | 2011-01-13 | 2014-10-01 | 福州大学 | Method for monitoring and analyzing concentration of nano-carbon material electrophoretic deposition liquid |
| CN102181867A (en) * | 2011-04-11 | 2011-09-14 | 江阴市润玛电子材料有限公司 | Novel acidic molybdenum aluminum etching liquid and preparation process thereof |
| CN102534621A (en) * | 2012-02-21 | 2012-07-04 | 上海正帆科技有限公司 | Method for treating acidic etching solution |
| CN102981523A (en) * | 2012-11-14 | 2013-03-20 | 杭州格林达化学有限公司 | Online determination and control method for concentrations of various acids in aluminum etching solution |
| CN103868866A (en) * | 2014-03-12 | 2014-06-18 | 深圳市华星光电技术有限公司 | Etching solution concentration measurement device and etching solution concentration measurement method |
| WO2015135230A1 (en) * | 2014-03-12 | 2015-09-17 | 深圳市华星光电技术有限公司 | Etching solution concentration measurement apparatus and method |
| CN105304462A (en) * | 2014-07-17 | 2016-02-03 | 株式会社平间理化研究所 | Etching liquid management device and method, and determination method of ingredient concentration of etching liquid |
| CN105278566A (en) * | 2014-07-17 | 2016-01-27 | 株式会社平间理化研究所 | Etching solution managing apparatus, dissolved metal concentration measuring apparatus and dissolved metal concentration measuring method |
| CN105304462B (en) * | 2014-07-17 | 2019-07-19 | 株式会社平间理化研究所 | The component concentration measuring method of etching liquid management device and method and etching solution |
| TWI682067B (en) * | 2014-07-17 | 2020-01-11 | 平間理化研究所股份有限公司 | Etching solution managing apparatus, etching solution managing method and concentration measuring method for component of etching solution |
| CN110383429A (en) * | 2017-03-27 | 2019-10-25 | 株式会社斯库林集团 | Substrate processing method using same and substrate board treatment |
| CN110383429B (en) * | 2017-03-27 | 2023-06-09 | 株式会社斯库林集团 | Substrate processing method and substrate processing apparatus |
| CN109923415A (en) * | 2019-01-24 | 2019-06-21 | 香港应用科技研究院有限公司 | System and method for determining material concentration in solution |
| US11340205B2 (en) | 2019-01-24 | 2022-05-24 | Hong Kong Applied Science And Technology Research Institute Co., Ltd. | Systems and methods for determining concentrations of materials in solutions |
| CN114428064A (en) * | 2021-12-31 | 2022-05-03 | 江苏和达电子科技有限公司 | Method for detecting content of nitrate ions in copper etching solution |
| CN114428064B (en) * | 2021-12-31 | 2023-09-19 | 江苏和达电子科技有限公司 | Method for detecting content of nitrate ions in copper etching solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5405042B2 (en) | 2014-02-05 |
| KR101213108B1 (en) | 2012-12-18 |
| JP2009266893A (en) | 2009-11-12 |
| TWI454872B (en) | 2014-10-01 |
| CN101567309B (en) | 2012-10-31 |
| TW201003348A (en) | 2010-01-16 |
| KR20090111765A (en) | 2009-10-27 |
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