CN100431113C - Etching liquid recovering system and method - Google Patents
Etching liquid recovering system and method Download PDFInfo
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- CN100431113C CN100431113C CNB200510003670XA CN200510003670A CN100431113C CN 100431113 C CN100431113 C CN 100431113C CN B200510003670X A CNB200510003670X A CN B200510003670XA CN 200510003670 A CN200510003670 A CN 200510003670A CN 100431113 C CN100431113 C CN 100431113C
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- etching
- etching solution
- impurity
- waste liquid
- recovery
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Abstract
The present invention discloses an etching solution recovery system which comprises an etching groove, an etching solution supplying device, an impurity removing device and a regulating device of mixed acid and concentration, wherein the etching groove is used for carrying out etching reactions which can generate waste liquid containing impurities, the etching solution supplying device is used for supplying an etching solution to the etching groove, the impurity removing device is used for receiving the waste liquid from the etching groove and removing the impurities in the waste liquid so as to form a recovery etching solution and the regulating device of mixed acid and concentration is used for carrying out regulating steps of the mixed acid and the concentration on the recovered etching solution.
Description
Technical field
The present invention relates to a kind of etching liquid recovering system and etching solution recovery method, and is specially adapted to the etch process of Thin Film Transistor-LCD.
Background technology
In Thin Film Transistor-LCD (TFT-LCD) and semiconductor technology, the normal metals such as aluminium, molybdenum that use are as electric conducting material, and often metals such as aluminium, molybdenum are carried out patterning in the wet etching mode, its etching solution can use multiple different acid, wherein the most universal etching solution is the mixed liquor with phosphoric acid, nitric acid and acetic acid, below is its reaction mechanism:
HNO
3+H
2O→H
3O
++NO
3 -
2Al+6H
+→2Al
3++3H
2
2Mo+6H
+→2Mo
3++3H
2
H
3PO
4+2H
2O→2H
3O
++HPO
4 2-
2Al
3++3HPO
4 2-→Al
2(HPO
4)
3→2AlPO
4+H
3PO
4
2Mo
3++3HPO
4 2-→Mo
2(HPO
4)
3→2MoPO
4+H
3PO
4
Wherein nitric acid is to play the part of H is provided
3O
+The role, carry out etching with the oxidized metal; And phosphoric acid provides phosphate radical, so that the metal of oxidation forms the misfit thing with phosphate radical respectively; Acetic acid suppresses nitric acid and dissociates and reach the adjustment of etch-rate and can be attached to reaction-ure surface.
And above-mentioned metal wet etching recovery system is shown in the 1st figure, at first the etching solution that mixes is supplied in the etching bath 10 by etching liquid supply device 11, carry out etching reaction with metal level to glass substrate, this etching solution can continue to handle the multi-disc glass substrate, so liquid etching composition and concentration can change, so when the impurity concentration in the etching solution during greater than to a certain degree (about 2000ppm) or etch processes behind certain glass-based plate number, be about to etching solution and all be expelled in the waste liquid accumulator tank 12, carry out outsourcing again and handle 13.
But because this etching solution is along with the increase of handling glass-based plate number, nitric acid wherein can continue to be consumed and impurity concentration also can be more and more higher, so etch effect and stability can be worse and worse and the variation of impurity concentration very big (0~2000ppm); In addition, when reaching 2000ppm, the etching solution impurity concentration carries out the discharging fully of etching solution, then newer etching solution is supplied in the etching bath 10 by etching liquid supply device 11, so the use amount of etching solution is very big, it is increasing to add the top glass substrate size, can make the demand of etching solution also increasing.
Summary of the invention
In view of this, purpose of the present invention once providing a kind of etching liquid recovering system and method, above-mentioned with other problem and reach better effect to solve.
For reaching above-mentioned purpose, the invention provides a kind of etching liquid recovering system, comprising: etching bath, in order to carrying out etching reaction, and etching reaction forms impure waste liquid; Etching liquid supply device is in order to supply etching solution to etching bath; Impurity removes device, in order to receive from the waste liquid of etching bath and to remove impurity in the waste liquid, reclaims etching solution to form; And nitration mixture and concentration regulator, in order to carry out nitration mixture and concentration set-up procedure to reclaiming etching solution; One waste liquid accumulator tank also should impure waste liquid drains into this impurity from this impure waste liquid of this etching bath and removes in the device in order to receive; One reclaims the etching solution accumulator tank, removes this recovery etching solution of device and should reclaim etching solution from this impurity in order to reception to drain in this nitration mixture and the concentration regulator; And an etching solution dashpot, also should reclaim etching solution and drained in this etching bath in order to receive this recovery etching solution from this nitration mixture and concentration regulator.
For reaching above-mentioned purpose, the present invention also provides a kind of etching solution recovery method, comprising: provide etching solution in etching bath, carrying out etching reaction, and etching reaction forms impure waste liquid; Remove the impurity that removes in the device in the waste liquid in impurity, reclaim etching solution to form; In nitration mixture and concentration regulator, carry out nitration mixture and concentration set-up procedure to reclaiming etching solution; And supply is reclaimed etching solution to etching bath.This method also comprises: in will this waste collection to the one waste liquid accumulator tank from this etching bath, and by this waste liquid accumulator tank this waste liquid is drained into this impurity and remove in the device; To be collected into one from this recovery etching solution that this impurity removes device and reclaim the etching solution accumulator tank, and should reclaim etching solution by this recovery etching solution accumulator tank and drain in this nitration mixture and the concentration regulator; And will be collected in the etching solution dashpot, and should reclaim etching solution by this etching solution dashpot and drained in this etching bath from this recovery etching solution of this nitration mixture and concentration regulator.
Description of drawings
Fig. 1 is a schematic diagram, in order to existing etching liquid recovering system to be described;
Fig. 2 is a schematic diagram, in order to the etching liquid recovering system of explanation one embodiment of the invention.
Symbol description
10,20~ etching bath 11,80~etching liquid supply device
12, the 13~outsourcing of 30~waste liquid accumulator tank is handled
40~impurity removes device 50~recovery etching solution accumulator tank
60~nitration mixture and concentration regulator 70~etching solution dashpot
90~single sour feeding mechanism
Embodiment
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, and conjunction with figs., be described in detail below:
Following embodiment is to be example with etching aluminium, and the present invention also can be used in molybdenum etching and other metal or its metal alloy etching.
At first etching solution is supplied in the etching bath 20 by etching liquid supply device 80, this etching solution comprises nitric acid, phosphoric acid and acetic acid.Then glass substrate is inserted in the etching bath 20, to carry out the aluminium etching reaction; Glass substrate after again etching being finished takes out, and then other is desired to carry out the etched glass substrate of aluminium and inserts in the etching bath 20, to carry out the aluminium etching reaction.Above-mentioned glass substrate etching and glass substrate displacement step will repeat for several times, after one the impurity of etching solution in etching bath 20 surpasses finite concentration or handled the glass substrate of a stator number, again the formed waste liquid that contains aluminium impurity partly or entirely is expelled in the waste liquid accumulator tank 30, the impurity concentration that contains aluminium impurity waste liquid when wherein waste liquid is discharged can decide according to different demands, as maximum contaminant limit, impurity concentration preset range, contain the discharge rate (ratio) of aluminium impurity waste liquid etc.If decide the discharge opportunity that contains aluminium impurity waste liquid according to the glass-based plate number of being handled, then this glass-based plate numerical value can decide according to experiment and result's statistics.Generally speaking, the more little or few more partly or entirely discharge of waste liquid that is about to contain aluminium impurity of processing glass-based plate number when impurity concentration, etch effect can be good more, but can make that producing and change the sour time increases, and then make the reduction of integral production efficient.
When the waste liquid that contains aluminium impurity in the waste liquid accumulator tank 30 is stored to certain volume, this waste liquid can be entered impurity and remove in the device 40.
Remove in the device 40 at impurity, contain impurity in the waste liquid of aluminium impurity and can be removed to a certain degree and reclaim etching solution, then again this is reclaimed etching solution and enter and reclaim in the etching solution accumulator tank 50 to form; Wherein impurity removes device 40 and can comprise amberplex, so that impurity is removed, as being that the etching solution that contains aluminium impurity that contains 73.1ppm aluminium impurity originally can get the recovery etching solution that aluminium impurity only contains 6ppm in 1.0 the environment after amberplex is handled at pH.Generally speaking, the rate of recovery of etching solution is more than 80%, and is roughly 80~90%.
Because etching solution is through the aluminium etching step time, phosphoric acid can form the misfit thing with aluminium, so the phosphoric acid in the etching solution can be lost, in addition, nitric acid and acetic acid also can be lost because etch processes, impurity remove processing or the like step, must could be supplied in the etching bath 20 once again through adjusting so reclaim etching solution again; Enter 60 li of nitration mixture and concentration regulators so next will reclaim recovery etching solution in the etching solution accumulator tank 50, after each sour concentration measurement, by nitric acid supply, phosphoric acid supply and acetic acid supply in single sour feeding mechanism the indivedual acid that lacked are mended again, be adjusted to and carry out in the etched scope will reclaim in the etching solution concentration of each acidic materials, again after mixing, just enter in the etching solution dashpot 70, and this dashpot 70 is waited for the demand of process equipment in order to store the etching solution of having finished the concentration adjustment; Next will reclaim etching solution again and enter in the etching bath, to carry out etch processes.
Because etching liquid recovering system of the present invention reclaims once again after can the impurity in removing waste liquid and uses, and the rate of recovery can reach more than 80%, thus can significantly reduce the consumption of etching solution, to reach the target of saving cost and environmental protection; In addition, the impurity concentration in the etching liquid recovering system may command etching solution of the present invention is in the stability range, and then the variation of minimizing etching reaction is to increase the process stabilizing degree; Moreover the framework of etching liquid recovering system of the present invention can make up other device and obtain in existing system, and promptly need not change existing system can obtain.
Though the present invention discloses preferred embodiment as above; right its is not in order to limit the present invention; any those skilled in the art can do change without departing from the spirit and scope of the present invention, so protection scope of the present invention should be as the criterion with claim institute restricted portion.
Claims (10)
1. etching liquid recovering system comprises:
One etching bath, in order to carrying out an etching reaction, and this etching reaction forms an impure waste liquid;
One etching liquid supply device is that supply one etching solution is to this etching bath;
One impurity removes device, is to receive this waste liquid and remove impurity in this waste liquid, and forms one and reclaim etching solution;
One nitration mixture and concentration regulator are that this recovery etching solution is carried out a nitration mixture and concentration set-up procedure;
One waste liquid accumulator tank also should impure waste liquid drains into this impurity from this impure waste liquid of this etching bath and removes in the device in order to receive;
One reclaims the etching solution accumulator tank, removes this recovery etching solution of device and should reclaim etching solution from this impurity in order to reception to drain in this nitration mixture and the concentration regulator; And
One etching solution dashpot also should reclaim etching solution and drained in this etching bath in order to receive this recovery etching solution from this nitration mixture and concentration regulator.
2. etching liquid recovering system as claimed in claim 1, wherein this impurity removes device and comprises amberplex.
3. etching liquid recovering system as claimed in claim 1, also comprise a single sour supply system, the sour supply system of this list comprises a phosphoric acid supply, a nitric acid supply and an acetic acid supply, in order to provide phosphoric acid, nitric acid and acetic acid respectively to this nitration mixture and concentration regulator and this etching bath.
4. etching liquid recovering system as claimed in claim 1 also comprises: a single sour supply system, and in order to provide acidic materials to this nitration mixture and concentration regulator and this etching bath.
5, a kind of etching solution recovery method comprises:
Provide an etching solution in an etching bath, carrying out an etching reaction, and this etching reaction forms an impure waste liquid;
Remove the impurity that removes in the device in this waste liquid in an impurity, reclaim etching solution to form one;
In a nitration mixture and concentration regulator, this recovery etching solution is carried out a nitration mixture and concentration set-up procedure; And
Supply this recovery etching solution to this etching bath,
Wherein this method also comprises:
In will this waste collection to one waste liquid accumulator tank, and by this waste liquid accumulator tank this waste liquid be drained into this impurity and remove in the device from this etching bath;
To be collected into one from this recovery etching solution that this impurity removes device and reclaim the etching solution accumulator tank, and should reclaim etching solution by this recovery etching solution accumulator tank and drain in this nitration mixture and the concentration regulator; And
To be collected in the etching solution dashpot from this recovery etching solution of this nitration mixture and concentration regulator, and should reclaim etching solution by this etching solution dashpot and drain in this etching bath.
6. etching solution recovery method as claimed in claim 5, wherein this etching reaction comprises that etching reactive aluminum, this waste liquid comprise that the etching solution and this impurity that contain aluminium impurity comprise aluminium misfit thing.
7. etching solution recovery method as claimed in claim 5, wherein this etching reaction comprises that the reaction of etching molybdenum, this waste liquid comprise that the etching solution and this impurity that contain molybdenum impurity comprise molybdenum misfit thing.
8. etching solution recovery method as claimed in claim 5, wherein this step that removes the impurity in this waste liquid is to utilize an amberplex.
9. etching solution recovery method as claimed in claim 5, the volume that wherein should reclaim etching solution be this waste liquid volume 80%~90%.
10. etching solution recovery method as claimed in claim 5, wherein this nitration mixture is for adding and mixing acidic materials with the concentration set-up procedure, these acidic materials are to select in the group that phosphoric acid, nitric acid, acetic acid and combination thereof are formed, and these acidic materials are provided by a single sour supply system, and the sour supply system of this list comprises the sour supply of a plurality of lists.
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CNB200510003670XA CN100431113C (en) | 2005-01-07 | 2005-01-07 | Etching liquid recovering system and method |
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CNB200510003670XA CN100431113C (en) | 2005-01-07 | 2005-01-07 | Etching liquid recovering system and method |
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CN100431113C true CN100431113C (en) | 2008-11-05 |
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CN103367197B (en) * | 2012-03-29 | 2015-12-02 | 无锡华瑛微电子技术有限公司 | Crystal column surface treatment system |
CN108427442A (en) * | 2017-02-12 | 2018-08-21 | 苏州耀群净化科技有限公司 | A kind of etchant concentration method of adjustment |
CN109148338A (en) * | 2018-09-04 | 2019-01-04 | 杭州中芯晶圆半导体股份有限公司 | A kind of method and device for improving etching machine nitration mixture and changing liquid efficiency |
Citations (7)
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US5275691A (en) * | 1991-02-28 | 1994-01-04 | Fuji Photo Film Co., Ltd. | Method for treating a surface of an aluminum substrate for a printing plate |
JPH0665763A (en) * | 1992-08-21 | 1994-03-08 | Tsurumi Soda Co Ltd | Device for treating waste etching liquid |
JP2000016810A (en) * | 1998-06-30 | 2000-01-18 | Nittetsu Mining Co Ltd | Production of aluminum sulfate having excellent solid- liquid separation from aluminum nitrate generated as by-product |
JP2000119891A (en) * | 1998-10-07 | 2000-04-25 | Zenken:Kk | Treating and recovering device for aqueous solution containing copper, sulfuric acid and nitric acid |
CN1348020A (en) * | 2000-10-10 | 2002-05-08 | 同济大学 | Method of eliminating nickel and heavy metal ion from waste ferric chloride liquid after etching or pickling |
CN1393418A (en) * | 2001-06-27 | 2003-01-29 | 三菱化学工程株式会社 | Method for supplying fluoric acid |
TW583342B (en) * | 2002-07-16 | 2004-04-11 | Hayashi Pure Chemical Ind Ltd | Method for recovering cerium from chromium etchant |
-
2005
- 2005-01-07 CN CNB200510003670XA patent/CN100431113C/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5275691A (en) * | 1991-02-28 | 1994-01-04 | Fuji Photo Film Co., Ltd. | Method for treating a surface of an aluminum substrate for a printing plate |
JPH0665763A (en) * | 1992-08-21 | 1994-03-08 | Tsurumi Soda Co Ltd | Device for treating waste etching liquid |
JP2000016810A (en) * | 1998-06-30 | 2000-01-18 | Nittetsu Mining Co Ltd | Production of aluminum sulfate having excellent solid- liquid separation from aluminum nitrate generated as by-product |
JP2000119891A (en) * | 1998-10-07 | 2000-04-25 | Zenken:Kk | Treating and recovering device for aqueous solution containing copper, sulfuric acid and nitric acid |
CN1348020A (en) * | 2000-10-10 | 2002-05-08 | 同济大学 | Method of eliminating nickel and heavy metal ion from waste ferric chloride liquid after etching or pickling |
CN1393418A (en) * | 2001-06-27 | 2003-01-29 | 三菱化学工程株式会社 | Method for supplying fluoric acid |
TW583342B (en) * | 2002-07-16 | 2004-04-11 | Hayashi Pure Chemical Ind Ltd | Method for recovering cerium from chromium etchant |
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