CN101122024A - Processing device for processing fluid and substrate processing device having the same - Google Patents

Processing device for processing fluid and substrate processing device having the same Download PDF

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Publication number
CN101122024A
CN101122024A CNA2007101046290A CN200710104629A CN101122024A CN 101122024 A CN101122024 A CN 101122024A CN A2007101046290 A CNA2007101046290 A CN A2007101046290A CN 200710104629 A CN200710104629 A CN 200710104629A CN 101122024 A CN101122024 A CN 101122024A
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China
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adsorption tower
elutriant
ablution
treatment solution
switching valve
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Chinese (zh)
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西川畅浩
田中幸雄
柏井俊彦
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SUMITOMO PRECISION INDUSTRY Co Ltd
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SUMITOMO PRECISION INDUSTRY Co Ltd
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Abstract

The present invention provides a substrate processing device which prolongs the replacing period of the processing liquid, prevents substrate processing efficiency from reducing and restrains substrate processing cost. The substrate processing device (1) comprises: a first processing liquid cycle mechanism (20) to ensure the processing liquid cycle between a storage trough (11) and a substrate processing mechanism (12); two absorption towers (32, 33), for absorbing metal ions contained in the processing liquid after the substrate processing of the substrate processing mechanism (12); a second processing liquid cycle mechanism (34), for supplying processing liquid of the storage trough (11) for arbitrary one of the absorption towers (32, 33) and ensuring the processing liquid cycle; and a control device (28), for controlling the motion of the second processing liquid cycly mechanism (34), so as to make the absorption towers (32, 33) be switched alternately based on prescribed time interval.

Description

Treatment solution treatment unit and the substrate board treatment that possesses this device
Technical field
The present invention relates to the treatment solution treatment unit and possess the substrate board treatment of this device, this treatment solution treatment unit is removed the processing of the metal ion that is contained in treatment solution in processing substrate.
Background technology
Production Example such as semi-conductor (silicon) wafer, liquid crystal glass base, photomask with glass substrate, the operation of CD with various substrates such as substrates in, comprise the operation of supplying with etching solution or various treatment solutions such as developing solution, ablution and this substrate being handled to these substrates.
And as the substrate board treatment that uses in this operation, known all the time for example have a disclosed etching system in the TOHKEMY 2000-96264 communique.This etching system comprises: the storagetank of storing etching solution; Substrate is carried out the processing substrate mechanism of etch processes by etching solution; The etching solution cycling mechanism is supplied with the etching solution that is stored in the storagetank to processing substrate mechanism, and reclaims the etching solution of having supplied with from this processing substrate mechanism, thereby etching solution is circulated between storagetank and processing substrate mechanism; Concentration sensor detects the concentration that helps the composition of etch processes in the etching solution that is stored in the storagetank; With etching solution supply establishment, if by the benchmark concentration of the detected deviation of concentration of concentration sensor regulation, the new etching solution of supply in storagetank then, thus make the above-mentioned favourable constituent concentration in this etching solution remain on finite concentration.
The aforesaid substrate processing mechanism comprises: the treatment chamber with enclosed space; A plurality of carrying rollers are provided in the treatment chamber, horizontal supporting substrate and to the prescribed direction conveyance; With a plurality of nozzle bodies etc., these a plurality of nozzle bodies are provided in the top of carrying roller, to the upper surface ejection etching solution of substrate.
Above-mentioned etching solution cycling mechanism comprises: supply-pipe, and one distolaterally is connected with storagetank, and another distolateral being located in the treatment chamber distolaterally is fixed with above-mentioned each nozzle body this another; Supply pump is supplied with etching solution by supply-pipe to each nozzle body; With recovery tube etc., one of this recovery tube distolaterally is connected with the bottom of above-mentioned treatment chamber, and another is distolateral to be connected with storagetank.
According to this etching system, to prescribed direction conveyance substrate, utilize supply pump by carrying roller simultaneously, supply with the etching solution that is stored in the storagetank by supply-pipe to each nozzle body, spray to upper surface of base plate from this each nozzle body, utilize this etching solution etching substrates.
And, circulate in recovery tube to the etching solution of upper surface of base plate ejection, in treatment chamber, be recycled in the storagetank.At any time detect the concentration of the above-mentioned favourable composition in the etching solution that is stored in the storagetank by concentration sensor, if depart from the benchmark concentration of regulation by the detected favourable constituent concentration of this concentration sensor, then utilize the new etching solution of etching solution supply establishment supply in storagetank, the above-mentioned favourable constituent concentration in this etching solution is remained on finite concentration.
Patent documentation 1: TOHKEMY 2000-96264 communique
But if for example the metallic membranes such as indium tin oxides film that form at the upper surface of substrate are carried out etching, then by this etching, constituting metals such as the indium of this metallic membrane and tin will be dissolved in the etching solution.Therefore, make in the etching solution above-mentioned existing etching system that the round-robin mode constitutes between storagetank and processing substrate mechanism, above-mentioned concentration of metal contained in the etching solution slowly rises, if this metal concentration reaches more than the certain level, will produce etching speed and descend, can't obtain problems such as high-precision etching shape.In addition, if above-mentioned concentration of metal contained in the etching solution rises, can produce the composition crystallization of the oxide compound that generates this metal in the etching solution, etching solution and separate out, this precipitate attached to the problem on the substrate, also can produce the problem that must regularly remove attached to the precipitate of storagetank internal surface attached to the internal surface of storagetank or with the particulate form.
Therefore, in above-mentioned existing etching system, must regularly replace the etching solution in the storagetank, and owing to can't carry out etch processes in the replacing process of etching solution, processing substrate efficient reduces.In addition, because of the reduction and the replacing expense (buying expenses of the waste treatment expense of the etching solution of having changed and the etching solution of replacing) that etching solution spent of this processing efficiency, the etch processes cost will increase.
Summary of the invention
The present invention finishes in view of above practical situation, its purpose be to provide a kind of can make the treatment solution treatment unit that treatment solution utilizes again and possess this treatment solution treatment unit and can prolong treatment solution replacement cycle, prevent that processing substrate efficient from reducing, suppressing the substrate board treatment of processing substrate cost.
In order to achieve the above object, the present invention relates to a kind of treatment solution treatment unit, be used for removing the processing of the contained metal ion of treatment solution that processing substrate uses, it is characterized in that, comprising:
Store the storagetank of above-mentioned treatment solution;
The adsorption of metal ions unit possesses at least two adsorption towers that are set up in parallel, and in the inside of this each adsorption tower, is filled with the sequestrant of the metal ion in the above-mentioned treatment solution of absorption; With
Remove to handle and use cycling element, have and be used for supplying with the treatment solution supply-pipe of the treatment solution in the above-mentioned storagetank, the treatment solution that is used in above-mentioned each adsorption tower, to circulate and be recycled to the treatment solution recovery tube in the above-mentioned storagetank and be arranged on the above-mentioned treatment solution supply-pipe and first switching valve of above-mentioned treatment solution is supplied with in control to above-mentioned each adsorption tower to above-mentioned each adsorption tower, by switching above-mentioned first switching valve, any one in above-mentioned each adsorption tower supplied with above-mentioned treatment solution and made its circulation selectively.
According to this treatment solution treatment unit, utilization is removed to handle and is used cycling element, be stored in treatment solution in the storagetank by any one supply in adsorption tower of treatment solution supply-pipe selectively, and after in this adsorption tower, circulating, be recycled in the storagetank by the treatment solution recovery tube, it is circulated between this storagetank and adsorption tower.In adsorption tower, by being filled in metal ion (being dissolved in the metal in the treatment solution) contained in its inner sequestrant adsorption treatment liquid.
The adsorption tower that is supplied to treatment solution is for example when judging metal by sequestrant absorption and reach roughly state of saturation, switch first switching valve by proper handling, thereby be converted to other adsorption tower, thus, the adsorptive power of the unitary metal ion of adsorption of metal ions can be kept certain.Moreover, if switch the adsorption tower be supplied to treatment solution, then stop to supply with treatment solution adsorption tower make the elutriant etc. of the metal wash-out that is adsorbed on the sequestrant, sequestrant is suitably regenerated.
Like this, the treatment in accordance with the present invention liquid processing device, circulate by making between treatment solution any one in storagetank and adsorption tower in the storagetank, can adsorb, remove the metal ion in the treatment solution, thereby this treatment solution is utilized again, therefore can save the expense of buying new treatment solution and the expense of the discarded treatment solution that uses etc., suppress the expense that etching solution spent, can reduce the cost that uses the processing substrate that this etching solution carries out.
In addition, by the switching of first switching valve, switch the adsorption tower that be supplied to treatment solution on one side, make the treatment solution circulation in the storagetank on one side, from treatment solution, do not remove metal ion so can not make the unitary adsorption of metal ions ability drop of adsorption of metal ions, can remove metal ion effectively.
In addition, above-mentioned treatment solution treatment unit also comprises: the elutriant feed unit, have and be used for supplying with wash-out absorption by the elutriant supply-pipe of the elutriant of the adsorbed metal of the sequestrant of stating each adsorption tower be arranged on the above-mentioned elutriant supply-pipe and second switching valve of above-mentioned elutriant is supplied with in control to above-mentioned each adsorption tower to this each adsorption tower, by switching above-mentioned second switching valve, any one in above-mentioned each adsorption tower supplied with above-mentioned elutriant selectively; Reclaim the unit with elutriant, be recovered in the elutriant after the circulation in above-mentioned each adsorption tower.And can constitute, by switching above-mentioned second switching valve, supply with above-mentioned elutriant to being in the above-mentioned adsorption tower that the supply that stops above-mentioned treatment solution and above-mentioned sequestrant be adsorbed with the metal ion state.
Like this, switch by removing first switching valve of handling with cycling element, then switch second switching valve of elutriant feed unit, supply with elutriant to the adsorption tower that stops the treatment solution supply by proper handling in case be supplied to the adsorption tower of treatment solution.By this elutriant and wash-out, the elutriant that contains the metal ion behind the wash-out reclaims the unit by elutriant and reclaims by the metal (metal ion) of the sequestrant of adsorption tower absorption.Can make sequestrant regeneration like this.In addition, be dissolved in very expensive metal is also arranged in the metal in the treatment solution, if can reclaim then very suitable, but, also can reclaim the metal that is dissolved in the treatment solution effectively by suitably reclaiming the metal ion in the elutriant that reclaims in the manner described above to it.
In addition, above-mentioned treatment solution treatment unit also comprises: the ablution feed unit, tool is capable to be used for supplying with the ablution supply-pipe of the ablution of cleaning above-mentioned each adsorption tower inside and being arranged on the above-mentioned ablution supply-pipe and the 3rd switching valve of above-mentioned ablution is supplied with in control to above-mentioned each adsorption tower to this each adsorption tower, by switching above-mentioned the 3rd switching valve, any one in above-mentioned each adsorption tower supplied with above-mentioned ablution selectively; With the ablution vent pipe, be used for discharging the ablution after the circulation in above-mentioned each adsorption tower to the outside.And can constitute, by switching above-mentioned the 3rd switching valve, the above-mentioned adsorption tower after elutriant is supplied with is supplied with above-mentioned ablution.
Like this, in case finished by the wash-out of the metal of sequestrant absorption, switch the 3rd switching valve of ablution feed unit by proper handling, the adsorption tower after elutriant is supplied with is supplied with ablution.Utilize this ablution to clean the inside of adsorption tower, this ablution is expelled to the outside from the ablution vent pipe.If elutriant remains in the inside of adsorption tower, when the treatment solution in the storagetank is supplied to this adsorption tower, this treatment solution mixes with elutriant, may bring detrimentally affect to the processing substrate of using treatment solution, but, by utilizing the ablution flush away to remain in elutriant in the adsorption tower, just can prevent the generation of this situation effectively.
In addition, above-mentioned treatment solution treatment unit can constitute, and also comprises the control unit that switches above-mentioned first switching valve according to pre-set time interval.In this case, the adsorption tower that is supplied to treatment solution passes through control unit, the timed interval according to the rules, promptly, according to inferring that metal by the sequestrant absorption of adsorption tower roughly reaches capacity timed interval of state, remove first switching valve of handling with cycling element by switching, change to other adsorption tower.Therefore, even adopt this structure, also the adsorptive power of the unitary metal ion of adsorption of metal ions can be kept certain, so can obtain and above-mentioned same effect.
In addition, above-mentioned treatment solution treatment unit can constitute, and also comprises: the concentration of metal ions detecting unit, detect the concentration of metal ions in the treatment solution that is stored in the above-mentioned storagetank; With when being higher than predefined benchmark value, switch the control unit of above-mentioned first switching valve by the detected concentration of metal ions of above-mentioned concentration of metal ions detecting unit.
In this case, the processing of removing that realizes by control unit is carried out in the following manner with the switching controls of first switching valve of cycling element.Promptly, if the metal by the absorption of the sequestrant of adsorption tower reaches roughly state of saturation, the adsorptive power of metal ion descends, concentration of metal ions in the treatment solution in the storagetank rises, be higher than specified reference value by the detected concentration of metal ions of concentration of metal ions detecting unit, then switch first switching valve, the adsorption tower that is supplied to treatment solution switches to other adsorption tower.
Therefore, even adopt above-mentioned structure, also the unitary adsorption of metal ions ability of adsorption of metal ions can be kept certain, so also can obtain and above-mentioned same effect.In addition, under the situation of the switching controls of carrying out first switching valve according to the elapsed time, according to as the concentration of removing metal ion contained in the treatment solution of process object, different by roughly reach capacity time of state of the metal of the sequestrant of adsorption tower absorption, therefore be difficult to set this switching time, but,, then can more effectively implement this switching controls by carrying out this switching controls according to the concentration of metal ions in the treatment solution in the storagetank.
In addition, under the situation of the switching controls of carrying out first switching valve by above-mentioned control unit according to elapsed time and concentration of metal ions, above-mentioned elutriant feed unit and elutriant can be set reclaim unit and above-mentioned ablution feed unit and ablution vent pipe, carry out the switching controls of the 3rd switching valve of second switching valve of this elutriant feed unit and ablution feed unit by this control unit.
In addition, the present invention relates to a kind of substrate board treatment, it is characterized in that, comprising:
Above-mentioned treatment solution treatment unit;
Utilize the processing unit of above-mentioned treatment solution treatment substrate; With
The processing substrate cycling element is supplied with the treatment solution that is stored in the above-mentioned storagetank to above-mentioned processing unit, and the treatment solution that will supply with is recycled to the above-mentioned storagetank from this processing unit, and treatment solution is circulated between above-mentioned storagetank and processing unit.
According to this substrate board treatment, utilize the processing substrate cycling element, the treatment solution that is stored in the storagetank is circulated between this storagetank and processing unit, in processing unit, use this treatment solution that substrate is suitably handled.On the other hand, in the round-robin treatment solution, in the treating processes of processing unit, contain metal ion (dissolving metal).And, if judging the concentration of metal ions in the treatment solution that is stored in the storagetank rightly raises, then utilize to remove to handle and use cycling element, make between treatment solution any one in this storagetank and adsorption tower in the storagetank and circulate, by the sequestrant adsorbing metal ions of adsorption tower.
Perhaps, the treatment solution in the storagetank circulates between this storagetank and processing unit with cycling element by processing substrate, and handles with circulating between cycling element any one in be everlasting this storagetank and adsorption tower by removing.Thus, in processing unit, use treatment solution to carry out processing substrate; And in adsorption tower, absorption is included in metal ion in the treatment solution by processing substrate.
And, in these cases also with above-mentioned same, suitably switch adsorption tower on one side, treatment solution is circulated on one side, make the adsorptive power of the unitary metal ion of adsorption of metal ions keep certain.In addition, if switch adsorption tower, the sequestrant that then stops the adsorption tower that treatment solution supplies with can use elutriant etc. suitably to regenerate.
Like this, according to substrate board treatment of the present invention, can adsorb, remove in processing substrate metal ion contained in the treatment solution, thereby treatment solution is utilized again, and can from treatment solution, remove metal ion and carry out processing substrate simultaneously, so, can prolong the work-ing life of treatment solution, prolong the replacement cycle of treatment solution, and, can suppress the processing substrate cost than the lowland owing to prolong the replacement cycle of treatment solution.
In addition, during utilizing processing unit to carry out processing substrate, if make also circulation constantly in adsorption tower of treatment solution, thereby then the concentration of metal ions in the treatment solution often can be suppressed at and prevent bad phenomenon below the certain level, and need not stop processing unit and make its non-stop run, thus, can improve yield rate and processing substrate efficient.In addition, owing to preventing that generating oxide compound by the metal ion in the treatment solution causes the one-tenth of treatment solution to analyze, therefore, precipitate can be with the particulate form attached on the substrate, and need not to remove the operation attached to the precipitate of storagetank internal surface.
Moreover in the aforesaid substrate treatment unit, the switching controls of above-mentioned first switching valve also can be carried out according to piece number of substrate processed in processing unit.At this moment, in the aforesaid substrate treatment unit, counting unit is set, this counting unit is counted piece number of the substrate handled by above-mentioned treatment solution in above-mentioned processing unit, when piece number of counting reaches predefined piece of number, to above-mentioned treatment solution treatment unit transmission switching signal.Simultaneously, in above-mentioned treatment solution treatment unit, be arranged on the control unit that when above-mentioned counting unit is accepted above-mentioned switching signal, switches above-mentioned first switching valve.
In this case, when piece number of the processing substrate in processing unit reaches regulation piece number, that is, when reaching deduction and reaching piece number of state of saturation roughly by the metal of the sequestrant of adsorption tower absorption, the adsorption tower that is supplied to treatment solution switches first switching valve by control unit.Therefore, even adopt this structure, also the adsorptive power of the unitary metal ion of adsorption of metal ions can be kept certain, so can obtain and above-mentioned same effect.
In addition, the aforesaid substrate treatment unit can constitute, and also comprises: favourable constituent concentration detecting unit is used for detecting the concentration that the row that is stored in the treatment solution in the above-mentioned storagetank is beneficial to the composition of aforementioned base processing; With the concentration adjustment unit,, adjust the above-mentioned favourable constituent concentration in the treatment solution that is stored in the above-mentioned storagetank, thereby remain in the predefined scope according to by the detected favourable constituent concentration of above-mentioned favourable constituent concentration detecting unit.
Like this, by the favourable constituent concentration in the treatment solution that is stored in the storagetank can being kept within the limits prescribed, so, can prevent that the processing substrate etc. because of processing unit from causing the favourable constituent concentration change of the treatment solution in the storagetank can't obtain problems such as predetermined process ability, and the processing substrate ability of treatment solution can be remained on optimum regime.
Wherein, as aforesaid substrate, for example can enumerate semi-conductor (silicon) wafer, liquid crystal glass base, photomask with glass substrate and CD with substrate etc., but also be not limited thereto.In addition, as above-mentioned treatment solution, can enumerate for example etching solution, developing solution and ablution etc., but also be not limited thereto.
In addition, generally, the material of the general designation aminocarboxylate that so-called chelaization agent is an organic system has adsorbing metal ions, and the metal that is adsorbed can be by the character of specific eluant solution.Particularly, can enumerate EDTA (ethylenediamine tetraacetic acid (EDTA)), NTA (triacetamide), DTPA (diethylene-triamine pentaacetic acid), GLDA (L-L-glutamic acid oxalic acid), HEDTA (hydroxyethylethylene diamine tri-acetic acid), GEDTA (glycoletherdiaminotetraacetic acid(GEDTA)), TTHA (triethylenetetramine six acetate), HIDA (hydroxyethyl imino-acetic acid) and DHEG (hydroxyethyl glycine) etc. as example, but also be not limited thereto.
The invention effect
As above above-mentioned, treatment in accordance with the present invention liquid processing device and substrate board treatment can adsorb, remove the metal ion in the treatment solution and this treatment solution is utilized again, can suppress the expense that treatment solution spends, and even the expense of processing substrate.In addition, the adsorptive power of metal ion is descended and from treatment solution, remove metal ion effectively.And, if treatment solution is also circulated in the adsorption tower of being everlasting, concentration of metal ions in the treatment solution not only can be suppressed at below the certain level, can also carry out processing substrate simultaneously continuously, and can prevent undesirable condition, can carry out processing substrate with lower cost.
Description of drawings
Fig. 1 is the structure iron that schematically shows the substrate board treatment structure of one embodiment of the present invention.
Fig. 2 is illustrated in the post chart that concerns between the concentration of indium ion contained in the amount of etching solution of logical liquid and the logical liquid after etching liquid.
Fig. 3 be behind the sulfuric acid amount that is illustrated in the post logical liquid, the logical liquid in the sulfuric acid concentration of contained indium ion and by the indium ion of sequestrant absorption by sulfuric acid and the chart of the relation between the ratio (eluting rate) of wash-out.
Fig. 4 is the structure iron that schematically shows the etching solution treatment unit structure of other embodiment of the present invention.
Nomenclature
1: substrate board treatment; 5: the etching solution treatment unit; 11: storagetank; 12: processing substrate mechanism; 20: the first etching solution cycling mechanisms; 24: concentration sensor; 25: the concentration adjustment mechanism; 28: control device; 28a: first control part; 28b: second control part; 30: remove mechanism; 31: adsorption of metal ions mechanism; 32: the first adsorption towers; 33: the second adsorption towers; 34: the second etching solution cycling mechanisms; 35: the etching solution supply-pipe; 36: supply pump; 37: the etching solution recovery tube; 38,39,40,41: switching valve; 42: the elutriant feed mechanism; 43: supply unit; 44: the elutriant supply-pipe; 45: the elutriant supply valve; 46,47: switching valve; 48: the elutriant recovering mechanism; 49: recoverer; 50: the elutriant recovery tube; 51,52: switching valve; 53: the elutriant recovery valve; 54: the ablution feed mechanism; 55: supply unit; 56: the ablution supply-pipe; 57: the ablution supply valve; 58: the ablution recovering mechanism; 59: recoverer; 60: the ablution recovery tube; 61: the ablution recovery valve; K: substrate; L: etching solution.
Embodiment
Below, with reference to the accompanying drawings the specific embodiment of the present invention is described.Wherein, Fig. 1 is the structure iron that schematically shows the substrate board treatment structure of one embodiment of the present invention.
As shown in Figure 1, this routine substrate board treatment 1 for example uses, and concentration of oxalic acid (weight %) is about 3% etching solution L, the substrate K that its upper surface is formed with indium tin oxides film (metallic membrane) carries out etch processes, comprising: store etching solution L storagetank 11, utilize etching solution L etching substrates K processing substrate mechanism 12, make etching solution L between storagetank 11 and processing substrate mechanism 12 the round-robin first etching solution cycling mechanism (etch processes cycling mechanism) 20, remove the indium that is dissolved among the etching solution L and tin (metal) remove mechanism 30 etc.
And aforesaid substrate treatment unit 1 comprises: detect the concentration of oxalic acid (concentration that helps the composition of etch processes) be stored in the etching solution L in the storagetank 11 concentration sensor 24, adjust concentration adjustment mechanism 25, control basal plate processing mechanism 12, the first etching solution cycling mechanism 20 of the concentration of oxalic acid that is stored in the etching solution L in the storagetank 11 and remove the control device 28 of the operation of mechanism 30 etc.Wherein, above-mentioned control device 28 comprises the first control part 28a of the control basal plate processing mechanism 12 and the first etching solution cycling mechanism 20 and controls and remove the second control part 28b of mechanism 30.And, in said structure, above-mentioned storagetank 11, remove mechanism 30 and the second control part 28b as etching solution treatment unit 5 performance functions.
Aforesaid substrate processing mechanism 12 comprises: the treatment chamber 13 that possesses enclosed space; A plurality of carrying rollers 14 are provided in the bottom in the treatment chamber 13, horizontal supporting and to prescribed direction (direction shown in the arrow) conveyance substrate K; Circulating tube 15 is provided in the top in the treatment chamber 13, and the etching solution L that is supplied with by the first etching solution cycling mechanism 20 circulates; With a plurality of nozzle bodies 16 etc., these a plurality of nozzle bodies are fixedly installed on the circulating tube 15, to the upper surface ejection etching solution L by the substrate K of carrying roller 14 conveyances.Etching solution L in the treatment chamber 13 discharges to the outside from the relief outlet 13a that the bottom surface in this treatment chamber 13 forms.
The above-mentioned first etching solution cycling mechanism 20 comprises: supply-pipe 21, is distolateral to be connected with storagetank 11, and another is distolateral to be connected with circulating tube 15; Supply pump 22, its operation is supplied with etching solution L by first control part 28a control by supply-pipe 21 in circulating tube 15; With recovery tube 23 etc., one of this recovery tube distolaterally is connected with the relief outlet 13a of treatment chamber 13, and another is distolateral to be connected with storagetank 11.
The above-mentioned mechanism 30 of removing comprises: adsorption of metal ions mechanism 31, and adsorb owing to the etch processes in the processing substrate mechanism 12 is dissolved among the etching solution L, and be contained in indium ion and tin ion (metal ion) among this etching solution L; The second etching solution cycling mechanism (remove to handle and use cycling mechanism) 34 circulates etching solution L between storagetank 11 and adsorption of metal ions mechanism 31; Elutriant feed mechanism 42, supply are used for wash-out by the indium of adsorption of metal ions mechanism 31 absorption and the elutriant of tin; Elutriant recovering mechanism 48 reclaims elutriant from adsorption of metal ions mechanism 31; Ablution feed mechanism 54 is supplied with the ablution that is used for cleaning adsorption of metal ions mechanism 31; With ablution recovering mechanism 58, reclaim ablution from adsorption of metal ions mechanism 31.
Above-mentioned adsorption of metal ions mechanism 31 comprises that inside is filled with at least two adsorption towers (first adsorption tower 32 and second adsorption tower 33) of the sequestrant (not shown) of absorption indium ion and tin ion.Wherein, generally, so-called chelaization agent (not shown) is the material of the general designation aminocarboxylate of organic system, has adsorbing metal ions, and the metal that is adsorbed can be by the character of specific eluant solution.Particularly, can enumerate EDTA (ethylenediamine tetraacetic acid (EDTA)), NTA (triacetamide), DTPA (diethylene-triamine pentaacetic acid), GLDA (L-L-glutamic acid oxalic acid), HEDTA (hydroxyethylethylene diamine tri-acetic acid), GEDTA (glycoletherdiaminotetraacetic acid(GEDTA)), TTHA (triethylenetetramine six acetate), HIDA (hydroxyethyl imino-acetic acid) and DHEG (hydroxyethyl glycine) etc. as example, but also be not limited thereto.
The above-mentioned second etching solution cycling mechanism 34 comprises: etching solution supply-pipe 35, is distolateral to be connected with storagetank 11, another distolateral branch and being connected with each adsorption tower 32,33; Supply pump 36, its operation is by second control part 28b control, by the internal feed etching solution L of etching solution supply-pipe 35 to each adsorption tower 32,33; Etching solution recovery tube 37, one is distolateral to be connected with storagetank 11, another distolateral branch and being connected with each adsorption tower 32,33; Be located at the first supply side switching valve 38 and the second supply side switching valve 39 of another distolateral branching portion of etching solution supply-pipe 35 respectively; The first discharge side switching valve 40 and second that is located at another distolateral branching portion of etching solution recovery tube 37 is respectively discharged side switching valve 41 etc.
Above-mentioned each switching valve 38,39,40,41 is by second control part 28b control, makes to discharge switching valve 40 when opening at the first supply side switching valve 38 and first, and the second supply side switching valve 39 and second discharges side switching valve 41 and cuts out; Discharge side switching valve 41 when opening at the second supply side switching valve 39 and second, the first supply side switching valve 38 and first discharges side switching valve 40 and cuts out.
In this second etching solution cycling mechanism 34, if drive supply pump 36, the adsorption tower 32,33 that is supplied to etching solution L will be supplied to 38,39 controls of side switching valve, and simultaneously, the etching solution L in the storagetank 11 is supplied in the adsorption tower 32,33 any one by etching solution supply-pipe 35.That is, open, when the second supply side switching valve 39 cuts out, supply with etching solution L to first adsorption tower 32 at the first supply side switching valve 38; Close at the first supply side switching valve 38, when the second supply side switching valve 39 is opened, supply with etching solution L to second adsorption tower 33.
And the etching solution L of any one supply in adsorption tower 32,33 and circulation in this adsorption tower 32,33 is recycled in the storagetank 11 from this adsorption tower 32,33 by etching solution recovery tube 37.
Above-mentioned elutriant feed mechanism 42 comprises: supply unit 43, and its operation is supplied with the elutriant that for example is made of hydrochloric acid or sulfuric acid by second control part 28b control; Elutriant supply-pipe 44, one is distolateral to be connected with supply unit 43, another distolateral branch and being connected with each adsorption tower 32,33; Elutriant supply valve 45, its operation be by second control part 28b control, and be located at the distolateral of elutriant supply-pipe 44; Be located at the first supply side switching valve 46 of another distolateral branching portion of elutriant supply-pipe 44 and second supply side switching valve 47 etc. respectively.Above-mentioned each switching valve 46,47 makes that by second control part 28b control the second supply side switching valve 47 cuts out when the first supply side switching valve 46 is opened; When the second supply side switching valve 47 was opened, the first supply side switching valve 46 cut out.
Above-mentioned elutriant recovering mechanism 48 comprises: the recoverer 49 that reclaims elutriant; Elutriant recovery tube 50, one is distolateral to be connected with recoverer 49, another distolateral branch and being connected with each adsorption tower 32,33; The first discharge side switching valve 51 and second that is located at another distolateral branching portion of elutriant recovery tube 50 is respectively discharged side switching valve 52; Elutriant recovery valves 53 etc., the operation of this elutriant recovery valve is controlled by the second control part 28b, and is located at the distolateral of elutriant recovery tube 50.Above-mentioned each switching valve 51,52 makes that by second control part 28b control second discharges side switching valve 52 closes when the first discharge side switching valve 51 is opened; When the second discharge side switching valve 52 was opened, first discharges side switching valve 51 closed.
In this elutriant feed mechanism 42 and elutriant recovering mechanism 48, if drive supply unit 43, the adsorption tower 32,33 that is supplied to elutriant is by 46,47 controls of supply side switching valve, simultaneously, elutriant is supplied to by elutriant supply-pipe 44 in the adsorption tower 32,33 any one from supply unit 43.That is, open, when the second supply side switching valve 47 cuts out, supply with elutriant to first adsorption tower 32 at the first supply side switching valve 46; Close at the first supply side switching valve 46, when the second supply side switching valve 47 is opened, supply with elutriant to second adsorption tower 33.
And the elutriant of any one supply in adsorption tower 32,33 and circulation in this adsorption tower 32,33 is recycled in the recoverer 49 from this adsorption tower 32,33 by elutriant recovery tube 50.And when the first supply side switching valve 46 was opened, first discharges side switching valve 51 opened, and second discharges side switching valve 52 closes; When the second supply side switching valve 47 was opened, second discharges side switching valve 52 opened, and first discharges side switching valve 51 closes.In addition, if drive supply unit 43, elutriant supply valve 45 and elutriant recovery valve 53 are opened.
Above-mentioned ablution feed mechanism 54 comprises: supply unit 55, and its operation is supplied with the ablution that for example is made of pure water by second control part 28b control; Ablution supply-pipe 56, one is distolateral to be connected with supply unit 55, and the branching portion of another distolateral and elutriant supply-pipe 44 and is connected between distolateral, and is connected with each adsorption tower 32,33 by this elutriant supply-pipe 44; Ablution supply valve 57, its operation is controlled by the second control part 28b, and is located on the ablution supply-pipe 56; With the above-mentioned first supply side switching valve 46 and the second supply side switching valve 47 etc.Above-mentioned each switching valve 46,47 and above-mentioned equally by second control part 28b control makes that the second supply side switching valve 47 cuts out when the first supply side switching valve 46 is opened; When the second supply side switching valve 47 was opened, the first supply side switching valve 46 cut out.
Above-mentioned ablution recovering mechanism 58 comprises: the recoverer 59 that reclaims ablution; Ablution recovery tube (ablution vent pipe) 60, one is distolateral to be connected with recoverer 59, is connected between branching portion of another distolateral and elutriant recovery tube 50 and the elutriant recovery valve 53, and is connected with each adsorption tower 32,33 by this elutriant recovery tube 50; Above-mentioned first discharges side switching valve 51 sharp second discharges side switching valve 52; With ablution recovery valve 61 etc., the operation of this ablution recovery valve is controlled by the second control part 28b, and it is distolateral to be located at another of ablution recovery tube 60.Above-mentioned each switching valve 51,52 and above-mentioned equally by second control part 28b control makes that second discharges side switching valve 52 closes when the first discharge side switching valve 51 is opened; When the second discharge side switching valve 52 was opened, first discharges switching valve 51 closed.
In this ablution feed mechanism 54 and ablution recovering mechanism 58, if drive supply unit 55, the adsorption tower 32,33 that is supplied to ablution is by 46,47 controls of supply side switching valve, simultaneously, ablution is supplied to the adsorption tower 32,33 any one from supply unit 55 by ablution supply-pipe 56 and elutriant supply-pipe 44.That is, open, when the second supply side switching valve 47 cuts out, supply with ablution to first adsorption tower 32 at the first supply side switching valve 46; Close at the first supply side switching valve 46, when the second supply side switching valve 47 is opened, supply with ablution to second adsorption tower 33.
And the ablution of any one supply in adsorption tower 32,33 and circulation in this adsorption tower 32,33 is recycled in the recoverer 59 from this adsorption tower 32,33 by elutriant recovery tube 50 and ablution recovery tube 60.And when the first supply side switching valve 46 was opened, first discharges switching valve 51 opened, and second discharges switching valve 52 closes; When the second supply side switching valve 47 was opened, second discharges switching valve 52 opened, and first discharges switching valve 51 closes.In addition, if drive supply unit 55, ablution supply valve 57 and ablution recovery valve 59 are opened.
Above-mentioned concentration adjustment mechanism 25 comprises: supply with for example supply unit 26 of oxalic acid and pure water etc. in storagetank 11; Supply-pipe 27, one is distolateral to be connected with supply unit 26, and another is distolateral to be connected with storagetank 11; With the above-mentioned first control part 28a etc., this first control part is according to by concentration sensor 24 detected concentration of oxalic acid, the operation of control supply unit 26.
The above-mentioned first control part 28a controls the supply pump 22 of the first etching solution cycling mechanism 20, and etching solution L is circulated between storagetank 11 and processing substrate mechanism 12.And the first control part 28a controls supply unit 26 according to by concentration sensor 24 detected concentration of oxalic acid, and the concentration of oxalic acid that is stored in the etching solution L in the storagetank 11 is remained in the predefined scope.For example, by concentration sensor 24 detected concentration of oxalic acid than the high situation of above-mentioned predefined scope under, supply with pure water to storagetank 11; By concentration sensor 24 detected concentration of oxalic acid than the low situation of above-mentioned predefined scope under, then supply with oxalic acid to storagetank 11, the concentration of oxalic acid that makes etching solution L is in predefined scope.Moreover the first control part 28a sends its coherent signal (commencing signal and end signal) at the circulation time that utilizes 20 beginnings of the first etching solution cycling mechanism and end etching solution L to the second control part 28b.
If the above-mentioned second control part 28b accepts above-mentioned commencing signal from the first control part 28a, then control supply pump 36 and each switching valve 38 of the second etching solution cycling mechanism 34,39,40,41, alternately switch the adsorption tower 32 that is supplied to etching solution L according to pre-set time interval on one side, 33, on one side to this adsorption tower 32, in 33 any one supplied with the etching solution L in the storagetank 11 and made its circulation, and in case switch the adsorption tower 32 that is supplied to etching solution L, 33, then at first control the supply unit 43 of elutriant feed mechanism 42, elutriant supply valve 45 and each switching valve 46,47 and each switching valve 51 of elutriant recovering mechanism 48,52 and elutriant recovery valve 53, to passing through to switch adsorption tower 32,33 and stop to supply with the adsorption tower 32 of etching solution L, supply with the elutriant of specified time in 33, then, the supply unit 54 of control ablution feed mechanism 54, ablution supply valve 57 and each switching valve 46,47 and each switching valve 51 of ablution recovering mechanism 58,52 and ablution recovery valve 61, carry out the processing of the ablution of supplying with the specified time.Moreover, if the second control part 28b accepts above-mentioned end signal from the first control part 28a, then stop to utilize the circulation of the etching solution L that the second etching solution cycling mechanism 34 carried out.
This routine substrate board treatment 1 according to above-mentioned structure, be stored in etching solution L in the storagetank 11 under the control of the first control part 28a, utilize the supply pump 22 of the first etching solution cycling mechanism 20, by supply-pipe 21 and circulating tube 15, be supplied to each nozzle body 16, from of the upper surface ejection of this each nozzle body 16 to substrate K.Then, the etching solution L that is ejected to substrate K upper surface circulates in recovery tube 23 and is recycled in the storagetank 11 from the relief outlet 13a of treatment chamber 13, so the etching solution L in the storagetank 11 circulate between this storagetank 11 and processing substrate mechanism 12.
Aforesaid substrate K, is utilized from the etching solution L (oxalic acid this etching solution L) of each nozzle body 16 ejection and carries out etching to the prescribed direction conveyance by carrying roller 14.And by this etch processes, the indium tin oxides film of substrate K is dissolved among the etching solution L, so contain indium ion and tin ion in this etching solution L.
In addition, be stored in etching solution L in the storagetank 11 under the control of the second control part 28b, utilize supply pump 36 and each switching valve 38,39 of the second etching solution cycling mechanism 34, be supplied to any one in the adsorption tower 32,33 selectively by etching solution supply-pipe 35, and circulation in this adsorption tower 32,33, then, be recycled in the storagetank 11, thereby it is circulated between this storagetank 11 and adsorption tower 32,33 by etching solution recovery tube 37.Thus, it is adsorbed that indium ion among the etching solution L and tin ion just are filled in the sequestrant (not shown) of adsorption tower 32,33 inside.
Be supplied to the adsorption tower 32,33 of etching solution L, by utilizing the second control part 28b to control each switching valve 38,39,40,41 of the second etching solution cycling mechanism 34, the timed interval according to the rules, promptly, reach by the indium of the sequestrant (not shown) of adsorption tower 32,33 absorption and tin according to inferring that roughly the timed interval of state of saturation alternately switches, if switch the adsorption tower 32,33 that is supplied to etching solution L, then utilize the second control part 28b to implement the following processing.
Promptly, at first, control each switching valve 51,52 and elutriant recovery valve 53 of supply unit 43, elutriant supply valve 45 and each switching valve 46,47 and the elutriant recovering mechanism 48 of elutriant feed mechanism 42 by the second control part 28b, elutriant will supply to by switching the adsorption tower 32,33 that adsorption tower 32,33 stops to supply with etching solution L by elutriant supply-pipe 44 from supply unit 43 and (when when first adsorption tower 32 switches to second adsorption tower 33, supply with to first adsorption tower 32 thus; And when second adsorption tower 33 switches to first adsorption tower 32, supply with to second adsorption tower 33), the elutriant of having supplied with circulates in this adsorption tower 32,33, then, is recycled in the recoverer 49 by elutriant recovery tube 50.Thus, by the indium of the sequestrant (not shown) of this adsorption tower 32,33 absorption and this elutriant of Xi Yin and wash-out contains the indium ion of wash-out and the elutriant of tin ion and is recovered in the recoverer 49.
Then, control each switching valve 51,52 and ablution recovery valve 61 of supply unit 54, ablution supply valve 57 and each switching valve 46,47 and the ablution recovering mechanism 58 of ablution feed mechanism 54 by the second control part 28b, ablution is supplied to the adsorption tower 32,33 identical with the adsorption tower 32,33 of supplying with above-mentioned elutriant from supply unit 55 by ablution supply-pipe 56 and elutriant supply-pipe 44 thus, the ablution of having supplied with circulates in this adsorption tower 32,33, then, be recycled in the recoverer 59 by elutriant recovery tube 50 and ablution recovery tube 60.Thus, remaining in the elutriant of these adsorption tower 32,33 inside will be by this ablution flush away.
Like this, if the adsorption tower of supplying with to the liquid L that stops etching 32,33 is supplied with elutriant and ablution successively, then become holding state after this adsorption tower 32,33.And so, be supplied to the adsorption tower 32,33 of etching solution L by switching, the indium ion of adsorption of metal ions mechanism 31 and the adsorptive power of tin ion can be kept certain, indium ion concentration and the tin ion concentration among the etching solution L can be suppressed at below the certain level.
Moreover the concentration of oxalic acid that is stored in the etching solution L in the storagetank 11 keeps within the limits prescribed by concentration adjustment mechanism 25.And, accept commencing signal to the process of accepting end signal, promptly from the second control part 28b, in the process of carrying out etch processes, etching solution L is constantly circulated in adsorption tower 32,33, from etching solution L, remove indium ion and tin ion, carry out etch processes simultaneously.
So, according to this routine substrate board treatment 1, during by the 12 etching substrates K of processing substrate mechanism, utilize the second etching solution cycling mechanism 34, alternately switch the adsorption tower 32,33 that is supplied to etching solution L on one side, make on one side in the storagetank 11 etching solution L and adsorption tower 32,33 in any one between often circulation, indium ion among the etching solution L and tin ion are adsorbed in the sequestrant (not shown) in this adsorption tower 32,33, if and switched the adsorption tower 32,33 of supplying with etching solution L, would then carry out following processing.Utilize elutriant feed mechanism 42 to supply with elutriant, make the indium and the tin wash-out that are adsorbed in the sequestrant (not shown), and this sequestrant (not shown) regenerated is handled to the adsorption tower 32,33 that the liquid L that stops etching supplies with; And utilizing the adsorption tower 32,33 of ablution feed mechanism 54 after elutriant is supplied with to supply with ablution, flush away remains in the processing of the elutriant of these adsorption tower 32,33 inside.Therefore, can remove indium ion and tin ion effectively, indium ion concentration among the etching solution L and tin ion concentration are suppressed at below the certain level, thereby it is bad to prevent etching, do not stop processing substrate mechanism 12 and make its non-stop run, prolong the life-span of etching solution L, prolong the replacement cycle of etching solution L.
In addition, if contain the indium ion of high density among the etching solution L, will be created in the problem that generates the composition oxalic acid crystallization among Indium sesquioxide, the etching solution L among the etching solution L and separate out, but, in this example, indium ion concentration among the etching solution L can be suppressed at below the certain level than the lowland, so can prevent separating out of oxalic acid.Therefore, the crystallisate of oxalic acid can be as particle and attached on the substrate K.In addition, can need not to remove operation attached to the oxalic acid crystallisate of storagetank 11 internal surfaces.
And by such enforcement successive etch processes, etch processes efficient can not descend, and the replacement cycle of etching solution L prolongs, and therefore also can suppress the etch processes cost than the lowland.
In addition, the adsorption tower 32,33 that is adsorbed with to the supply that is in the liquid L that stops etching and sequestrant (not shown) under the state of indium ion and tin ion is supplied with elutriants, and will contain the indium ion of capable wash-out and the elutriant of tin ion is recovered in the recoverer 49, therefore, can make this sequestrant (not shown) regeneration, simultaneously, the sharp tin ion of indium ion in the elutriant after this reclaims by suitable recovery can reclaim the indium (very Ang Gui metal) and the tin that are dissolved among the etching solution L effectively.
In addition, taking off liquid feed mechanism 42 supplies with after the elutriant, supply with ablution by ablution feed mechanism 54 to the adsorption tower 32,33 of supplying with elutriant, remain in the elutriant of these adsorption tower 32,33 inside with flush away, therefore, etching solution L in storagetank 11 is supplied to this adsorption tower 32,33 o'clock, can prevent from this etching solution L effectively and remain in elutriant in the adsorption tower 32,33 to mix the composition that makes etching solution L and change and the etch processes of being carried out in the processing substrate mechanism 12 is brought detrimentally affect.
And, by concentration adjustment mechanism 25, the concentration of oxalic acid that is stored in the etching solution L in the storagetank 11 is kept within the limits prescribed, therefore, the problems such as etch capabilities that the etch processes etc. because of being carried out makes the concentration of oxalic acid change of the etching solution L in the storagetank 11 obtain to stipulate can be prevented in processing substrate mechanism 12, and the etch processes ability of this etching solution L optimum regime can be remained on.
Below, the result who " キ レ ス ト Off ァ ィ バ one GRY-L (trade name) " that uses CHELEST CORPORATION to produce is carried out the adsorption experiment of metal ion as sequestrant describes.
Promptly, at first, preparing internal diameter is the post of 1.5cm, in this post, fill the above-mentioned sequestrant of heavy 4g, high 11cm, volume 19.4mL, then, make specified amount contain oxalic acid and for the etching solution that contains metal ion of etch processes with distolateral from above-mentioned post of the flow velocity of 3mL/min to another distolateral logical liquid.
Like this, after the logical liquid of etching solution of specified amount, etching solution by above-mentioned post is taken a sample, mensuration contains the concentration of metal ion, so draw following result, the indium ion concentration of the etching solution before the logical liquid is that 277ppm, tin ion concentration are that 33.7ppm, aluminium ion concentration are 0.24ppm, relative therewith, the indium ion concentration of the etching solution behind the logical liquid of post is that 8ppm, tin ion concentration are that 0.1ppm is following, aluminium ion concentration is below the 0.1ppm, each metal ion to the utmost point low concentration that all descends.
Hence one can see that, utilizes sequestrant can remove the metal ions such as indium ion, tin ion and aluminum ion that are present in the etching solution effectively.
In addition, use post and sequestrant same as described above, supply with etching solution same as described above and make its logical liquid in post according to flow velocity same as described above, whenever logical liquid is a certain amount of, etching solution behind the logical liquid is taken a sample, measure the concentration of indium ion contained in the etching solution after this circulation.Fig. 2 represents its result.Wherein, in Fig. 2, (Bed Volume: be the volume that is filled in the sequestrant in the post bed volume), (mL)/(mL-fiber) be (amount of the etching solution of logical liquid in post)/(being filled in the volume of the sequestrant in the post) to BV.Therefore, transverse axis represents how much logical liquid is equivalent to the etching solution of the amount of sequestrant volume.
As shown in Figure 2, till the logical liquid measure at etching solution reaches specified amount (the about 11 times amount that is equivalent to the sequestrant volume), do not detect indium ion from the etching solution after the circulation, the indium ion agent that is chelated fully is adsorbed.And as can be known, even if volume is supplied with etching solution, the adsorptive power of sequestrant can not descend yet.
Below, the experimental result of this metal ion of wash-out from the sequestrant that is adsorbed with metal ion is as mentioned above described.
That is, use post and sequestrant same as described above, in post, supply with the etching solution of specified amount same as described above and make its logical liquid, make to be adsorbed with in the sequestrant after the indium ion, make 1 normal sulfuric acid (1N-H according to flow velocity same as described above 2SO 4) with distolateral to another distolateral logical liquid from this post of the flow velocity of 1.5mL/min, whenever logical liquid is a certain amount of, the sulfuric acid behind the logical liquid is taken a sample, and measure the concentration of indium ion contained in the sulfuric acid after this circulation.Fig. 3 represents its result.Wherein, in Fig. 3, (Bed Volume: be the volume that is filled in the sequestrant in the post bed volume), (mL)/(mL-fiber) be (the vitriolic amount of logical liquid in post)/(being filled in the volume of the sequestrant in the post) to BV.Therefore, transverse axis represents how much logical liquid is equivalent to the sulfuric acid of the amount of sequestrant volume.
In addition, in the mensuration of the indium ion concentration in above-mentioned, the long-pending conduct of the indium ion concentration of each time point till will can't confirming to have indium ion in the sulfuric acid after the circulation and the logical liquid measure of this time band is calculated in the indium ion amount of each time point wash-out, and this aggregate-value obtained as the amount of whole indiums of wash-outs, the value defined that will obtain divided by the amount of the indium of these whole wash-outs with the amount of the indium of each time point wash-out is represented in Fig. 3 in the lump at the eluting rate of each time point (by the indium of sequestrant absorption by the ratio of sulfuric acid wash-out).
By this Fig. 3 as can be known, utilize the indium of sulfuric acid wash-out by sequestrant absorption, and, if the logical liquid measure of vitriolic reaches specified amount (the about 2.8 times amount that is equivalent to the sequestrant volume), then by the indium of sequestrant absorption wash-out fully.And use sulfuric acid can make the sequestrant regeneration that is adsorbed with indium effectively, and use sulfuric acid can also reclaim the metal of the agent absorption that is chelated effectively.
More than, one embodiment of the present invention are illustrated, still, the adoptable concrete mode of the present invention is not limited thereto.
In the above example, constituting with specific time hands over symbol to switch the adsorption tower 32,33 of supplying with etching solution L at interval, but it is also not limited thereto, for example, also can constitute, carry out the switching controls of adsorption tower 32,33 according to piece number of etched substrate K in processing substrate mechanism 12, perhaps the switching controls of carrying out adsorption tower 32,33 according to the indium ion concentration among the etching solution L that is stored in the storagetank 11 and tin ion concentration.
Carry out under the situation of switching controls at etching piece number according to substrate K, aforesaid substrate processing mechanism 12 constitutes, for example also comprise transmitter (not shown), this transmitter is provided in suitable positions such as the outside of treatment chamber 13 or inside, detects substrate K that moves in the treatment chamber 13 or the substrate K that takes out of from treatment chamber 13.The above-mentioned first control part 28a constitutes, also performance is as the function of the counting unit that piece number of etched substrate K in processing substrate mechanism 12 is counted, and carry out following processing: according to the output signal that obtains from the sensor (not shown), the processing that piece number (piece number of etched substrate K in processing substrate mechanism 12) of piece number of moving into the substrate K in the treatment chamber 13 or the substrate K that takes out of from treatment chamber 13 is counted; Except above-mentioned commencing signal and end signal, also send the processing of the signal (switching signal) when piece number of above-mentioned counting reaches predefined piece of number to the second control part 28b.The above-mentioned second control part 28b constitutes, control supply pump 36 and each switching valve 38,39,40,41 of the second etching solution cycling mechanism 34, when the first control part 28a accepts switching signal, switch on one side the adsorption tower 32,33 that is supplied to etching solution L, on one side in this adsorption tower 32,33 any one supply with the etching solution L in storagetank 11 and make its circulation.And the first control part 28a constitutes, if piece number of above-mentioned counting reaches predefined piece of number, count value is resetted, and counts up to predefined piece of number once more.And the second control part 28b utilizes the second etching solution cycling mechanism 34 to make etching solution L circulation from accepting commencing signal during accept end signal.
If constitute substrate board treatment 1 in the above described manner, so, when piece number of counting reaches predefined piece of number, promptly, become and infer when reaching piece number of state of saturation roughly by the indium of the sequestrant (not shown) of adsorption tower 32,33 absorption and tin, switch each switching valve 38,39,40,41, switch the adsorption tower 32,33 that is supplied to etching solution L.
Therefore, even constitute substrate board treatment 1 in the manner described above, also the indium ion of adsorption of metal ions mechanism 31 and the adsorptive power of tin ion can be kept certain, indium ion concentration among the etching solution L and tin ion concentration are suppressed at below the certain level, therefore, can obtain and above-mentioned same effect.
On the other hand, carrying out under the situation of switching controls according to indium ion concentration and tin ion concentration, above-mentioned etching solution treatment unit 5 constitutes, also comprise the indium ion concentration that detects among the etching solution L be stored in the storagetank 11 and/or the concentration of metal ions detecting sensor (not shown) of tin ion concentration, the above-mentioned second control part 28b constitutes, control supply pump 36 and each switching valve 38 of the second etching solution cycling mechanism 34,39,40,41, when being higher than predefined benchmark value by detected indium ion concentration of concentration of metal ions detecting sensor (not shown) and/or tin ion concentration, switch the adsorption tower 32 that is supplied to etching solution L on one side, 33, Yi Bian to this adsorption tower 32, in 33 any one supplied with the etching solution L in the storagetank 11 and made its circulation.
If constitute substrate board treatment 1 in the above described manner, the indium and the tin that adsorb as if the sequestrant (not shown) by adsorption tower 32,33 reach roughly state of saturation, the adsorptive power of indium ion and tin ion descends, the indium ion concentration and the tin ion concentration that are stored among the etching solution L in the storagetank 11 rise, be higher than specified reference value by detected indium ion concentration of concentration of metal ions detecting sensor (not shown) and/or tin ion concentration, so, switch each switching valve 38,39,40,41, switch the adsorption tower 32,33 that is supplied to etching solution L.
Therefore, even constitute substrate board treatment 1 in the above described manner, also the indium ion of adsorption of metal ions mechanism 31 and the adsorptive power of tin ion can be kept certain, indium ion concentration and tin ion concentration among the etching solution L can be suppressed at below the certain level, so can obtain and above-mentioned same effect.In addition, carrying out adsorption tower 32 according to an elapsed time or an etching piece number, under the situation of 33 switching controls, according to the etching condition in the processing substrate mechanism 12 with as kind of the substrate K of etch target etc., the meltage that is dissolved in indium among the etching solution L and tin is different, by adsorption tower 32, it is different with etching piece number that the indium of 33 sequestrant (not shown) absorption and tin reach the time of state of saturation roughly, so, be difficult to set this switching time and etching piece number, but, by carrying out adsorption tower 32 according to indium ion concentration and/or tin ion concentration among the etching solution L in the storagetank 11,33 switching controls then can more effectively be implemented adsorption tower 32,33 switching controls.
In addition, in above-mentioned example, in processing substrate mechanism 12 during the etching substrates K, make etching solution L circulation in adsorption tower 32,33 constantly, but it is also not limited thereto, for example, also can the elapsed time of instrument after the beginning etch processes reach the specified time, perhaps the etching of a substrate K piece number reaches regulation piece number, when perhaps indium ion concentration among the etching solution L in the storagetank 11 and tin ion concentration surpass normality, etching solution L is circulated in adsorption tower 32,33 for removing indium ion and tin ion.
In addition, in above-mentioned example, in substrate board treatment 1, be provided with etching solution treatment unit 5, but not limited thereto, for example also can be etching solution treatment unit 6 shown in Figure 4.This etching solution treatment unit 6 constitutes by removing the storagetank 70, above-mentioned mechanism 30 and the above-mentioned second control part 28b etc. of removing that handle usefulness.In above-mentioned storagetank 70, the storagetank 11 that the etching from be attached to processing substrate mechanism 12 is used is suitably collected the etching solution L that finishes using.Moreover, in etching solution treatment unit 6 shown in Figure 4, the component part mark identical symbol identical with substrate board treatment shown in Figure 11, and omit its detailed explanation.
In this case, etching solution L in the storagetank 70 is under the control of the second control part 28b, by circulating between the second etching solution cycling mechanism 34 any one in storagetank 70 and adsorption tower 32,33, the sequestrant (not shown) that indium ion among the etching solution L and tin ion are adsorbed tower 32,33 adsorbs, removes.At this moment, for example according to the rules timed interval is alternately switched the adsorption tower 32,33 that is supplied to etching solution L.
And, begin through certain hour from the etching solution L that to adsorption tower 32,33, supplies with in the storagetank 70, if indium ion concentration and the tin ion concentration of the etching solution L in the storagetank 70 are lower than predefined benchmark value, so, the stop etching circulation of liquid L, the processing of removing of indium ion and tin ion finishes.Then, the etching solution L after the processing of removing in the storagetank 70 suitably flows back in the storagetank 11 that etching uses.
Moreover, utilize elutriant feed mechanism 42 in the switching by adsorption tower 32,33 stops to supply with the adsorption tower 32,33 of etching solution L, to supply with elutriant, utilize ablution feed mechanism 54 to supply with ablutions then, the elutriant of having supplied with is recovered respectively by ablution recovering mechanism 58 by elutriant recovering mechanism 48, the ablution supplied with.
By this etching solution treatment unit 6, by the etching solution L in the storagetank 70 is circulated between storagetank 70 and adsorption tower 32,33, also can adsorb and remove indium ion and tin ion among the etching solution L, thereby this etching solution L is utilized again, so, can save the expense of buying new etching solution L and the expense of discarding the etching solution L that uses etc., thereby can suppress the expense that etching solution L is spent, can reduce the cost of etch processes.
In addition, owing to switch the adsorption tower 32,33 that is supplied to etching solution L on one side, make the etching solution L circulation in the storagetank 70 on one side, therefore, the adsorptive power of the indium ion of adsorption tower 32,33 and tin ion is reduced and can from etching solution L, remove indium ion and tin ion can be removed indium ion and tin ion effectively.
In addition, in above-mentioned example, use concentration of oxalic acid to be about 3% etching solution L, the substrate K that upper surface is formed with indium tin oxides film carries out etch processes, and reclaim the indium and the tin that are dissolved among the etching solution L, but the metal species of the kind of etching solution L and recovery is not limited thereto.
In addition, in above-mentioned example, constitute in the mode of substrate K being carried out etch processes, but also can carry out development treatment or clean processing etc., in addition, substrate K comprise semi-conductor (silicon) wafer, liquid crystal glass base, photomask with glass substrate and CD with various substrate K such as substrates.And, the adsorption tower 32,33 that above-mentioned adsorption of metal ions mechanism 31 also can possess more than three.
In addition, in above-mentioned example, constitute, carry out each switching valve 38 of the second etching solution cycling mechanism 34 by the second control part 28b, 39,40,41, the supply unit 43 of elutriant feed mechanism 42, elutriant supply valve 45 and each switching valve 46,47, each switching valve 51 of elutriant recovering mechanism 48,52 and elutriant recovery valve 53, the supply unit 54 of ablution feed mechanism 54, ablution supply valve 57 and each switching valve 46,47, each switching valve 51 of ablution recovering mechanism 58,52 and the operation of ablution recovery valve 61 control, also can adopt the manually operated mode of operator to constitute.
In addition, in above-mentioned example, constitute above-mentioned control device 28 by the first control part 28a and the second control part 28b, but also not limited thereto, also can make a control part have the function of the first control part 28a and the function of the second control part 28b.

Claims (12)

1. treatment solution treatment unit is used for removing the processing of the contained metal ion of treatment solution that processing substrate uses, it is characterized in that, comprising:
Store the storagetank of described treatment solution;
The adsorption of metal ions unit possesses at least two adsorption towers that are set up in parallel, and in the inside of this each adsorption tower, is filled with the sequestrant of the metal ion in the described treatment solution of absorption; With
Remove to handle and use cycling element, have and be used for supplying with the treatment solution supply-pipe of the treatment solution in the described storagetank, the treatment solution that is used in described each adsorption tower, to circulate and be recycled to the treatment solution recovery tube in the described storagetank and be arranged on the described treatment solution supply-pipe and first switching valve of described treatment solution is supplied with in control to described each adsorption tower to described each adsorption tower, by switching described first switching valve, any one in described each adsorption tower supplied with described treatment solution and made its circulation selectively.
2. treatment solution treatment unit as claimed in claim 1 is characterized in that:
Also comprise: the elutriant feed unit, have and be used for supplying with wash-out by the elutriant supply-pipe of the elutriant of the metal of the sequestrant absorption of described each adsorption tower be arranged on the described elutriant supply-pipe and second switching valve of described elutriant is supplied with in control to described each adsorption tower to this each adsorption tower, by switching described second switching valve, any one in described each adsorption tower supplied with described elutriant selectively; With
Elutriant reclaims the unit, is recovered in the elutriant of circulation in described each adsorption tower,
And constitute, by switching described second switching valve, supply with described elutriant to being in the described adsorption tower that the supply that stops described treatment solution and described sequestrant be adsorbed with the metal ion state.
3. treatment solution treatment unit as claimed in claim 2 is characterized in that:
Also comprise: the ablution feed unit, have and be used for supplying with the ablution supply-pipe of the ablution of cleaning described each adsorption tower inside and being arranged on the described ablution supply-pipe and the 3rd switching valve of described ablution is supplied with in control to described each adsorption tower to this each adsorption tower, by switching described the 3rd switching valve, any one in described each adsorption tower supplied with described ablution selectively; With
The ablution vent pipe is used for discharging the ablution that circulates to the outside in described each adsorption tower,
And constitute, by switching described the 3rd switching valve, the described adsorption tower after elutriant is supplied with is supplied with described ablution.
4. treatment solution treatment unit as claimed in claim 1 is characterized in that:
Also comprise the control unit that switches described first switching valve according to pre-set time interval.
5. treatment solution treatment unit as claimed in claim 1 is characterized in that, also comprises:
The concentration of metal ions detecting unit detects the concentration of metal ions in the treatment solution that is stored in the described storagetank; With
When being higher than predefined benchmark value, switch the control unit of described first switching valve by the detected concentration of metal ions of described concentration of metal ions detecting unit.
6. as claim 4 or 5 described treatment solution treatment unit, it is characterized in that:
Also comprise: the elutriant feed unit, have and be used for supplying with wash-out by the elutriant supply-pipe of the elutriant of the metal of the sequestrant absorption of described each adsorption tower be arranged on the described elutriant supply-pipe and second switching valve of described elutriant is supplied with in control to described each adsorption tower to this each adsorption tower, by switching described second switching valve, any one in described each adsorption tower supplied with described elutriant selectively; With
Elutriant reclaims the unit, is recovered in the elutriant of circulation in described each adsorption tower,
And described control unit constitutes, if switch described first switching valve, then switches described second switching valve, supplies with described elutriant to being in the described adsorption tower that the supply that stops described treatment solution and described sequestrant be adsorbed with the metal ion state.
7. treatment solution treatment unit as claimed in claim 6 is characterized in that:
Also comprise: the ablution feed unit, have and be used for supplying with the ablution supply-pipe of the ablution of cleaning described each adsorption tower inside and being arranged on the described ablution supply-pipe and the 3rd switching valve of described ablution is supplied with in control to described each adsorption tower to this each adsorption tower, by switching described the 3rd switching valve, any one in described each adsorption tower supplied with described ablution selectively; With
The ablution vent pipe is used for discharging the ablution that circulates to the outside in described each adsorption tower,
And described control unit constitutes, if finish the supply of described elutriant, then switches described the 3rd switching valve, and the described adsorption tower after elutriant is supplied with is supplied with described ablution.
8. a substrate board treatment is characterized in that, comprising:
Each described treatment solution treatment unit in the claim 1～7;
Utilize the processing unit of described treatment solution treatment substrate; With
The processing substrate cycling element is supplied with the treatment solution that is stored in the described storagetank to described processing unit, and the treatment solution that will supply with is recycled to the described storagetank from this processing unit, and treatment solution is circulated between described storagetank and processing unit.
9. substrate board treatment is characterized in that:
Comprise: the described treatment solution treatment unit of claim 1;
Utilize the processing unit of described treatment solution treatment substrate;
The processing substrate cycling element is supplied with the treatment solution that is stored in the described storagetank to described processing unit, and the treatment solution of supplying with is recycled to the described storagetank from this processing unit, and treatment solution is circulated between described storagetank and processing unit; With
Counting unit is counted piece number of the substrate handled by described treatment solution in described processing unit, when piece number of counting reaches predefined piece of number, and to described treatment solution treatment unit transmission switching signal,
And described treatment solution treatment unit also is included in the control unit that switches described first switching valve when described counting unit is accepted described switching signal.
10. substrate board treatment as claimed in claim 9 is characterized in that:
Described treatment solution treatment unit also comprises: the elutriant feed unit, have and be used for supplying with wash-out by the elutriant supply-pipe of the elutriant of the metal of the sequestrant absorption of described each adsorption tower be arranged on the described elutriant supply-pipe and second switching valve of described elutriant is supplied with in control to described each adsorption tower to this each adsorption tower, by switching described second switching valve, any one in described each adsorption tower supplied with described elutriant selectively; With
Elutriant reclaims the unit, is recovered in the elutriant of circulation in described each adsorption tower,
And described control unit constitutes, if switch described first switching valve, then switches described second switching valve, supplies with described elutriant to being in the described adsorption tower that the supply that stops described treatment solution and described sequestrant be adsorbed with the metal ion state.
11. substrate board treatment as claimed in claim 10 is characterized in that:
Described treatment solution treatment unit also comprises: the ablution feed unit, have and be used for supplying with the ablution supply-pipe of the ablution of cleaning described each adsorption tower inside and being arranged on the described ablution supply-pipe and the 3rd switching valve of described ablution is supplied with in control to described each adsorption tower to this each adsorption tower, by switching described the 3rd switching valve, any one in described each adsorption tower supplied with described ablution selectively; With
The ablution vent pipe is used for discharging the ablution that circulates to the outside in described each adsorption tower,
And described control unit constitutes, if finish the supply of described elutriant, then switches described the 3rd switching valve, and the described adsorption tower after elutriant is supplied with is supplied with described ablution.
12. as each described substrate board treatment in the claim 8～11, it is characterized in that, also comprise:
Favourable constituent concentration detecting unit is used for detecting the concentration that the row that is stored in the treatment solution in the described storagetank is beneficial to the composition of described processing substrate; With
The concentration adjustment unit according to by the detected favourable constituent concentration of described favourable constituent concentration detecting unit, is adjusted the described favourable constituent concentration in the treatment solution that is stored in the described storagetank, thereby is remained in the predefined scope.
CNA2007101046290A 2006-05-18 2007-05-18 Processing device for processing fluid and substrate processing device having the same Pending CN101122024A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006138595 2006-05-18
JP2006138595 2006-05-18
JP2007058249 2007-03-08
JP2007101392 2007-04-09

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Publication Number Publication Date
CN101122024A true CN101122024A (en) 2008-02-13

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CN102154648A (en) * 2010-02-12 2011-08-17 住友精密工业株式会社 Etching method
CN102629549A (en) * 2011-06-01 2012-08-08 北京京东方光电科技有限公司 Wet etching equipment and method thereof
CN103065958A (en) * 2011-08-31 2013-04-24 住友精密工业股份有限公司 Chelating material regeneration method and substrate processing device
CN108428645A (en) * 2017-02-15 2018-08-21 东京毅力科创株式会社 substrate liquid processing device
CN109071104A (en) * 2016-03-31 2018-12-21 富士胶片株式会社 The manufacturing method of semiconductors manufacture treatment fluid, the accepting container for containing semiconductors manufacture treatment fluid, pattern forming method and electronic device
CN111415883A (en) * 2019-01-08 2020-07-14 东京毅力科创株式会社 Substrate processing apparatus, substrate processing method, and storage medium
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102154648A (en) * 2010-02-12 2011-08-17 住友精密工业株式会社 Etching method
CN102629549A (en) * 2011-06-01 2012-08-08 北京京东方光电科技有限公司 Wet etching equipment and method thereof
CN102629549B (en) * 2011-06-01 2015-05-13 北京京东方光电科技有限公司 Wet etching equipment and method thereof
CN103065958A (en) * 2011-08-31 2013-04-24 住友精密工业股份有限公司 Chelating material regeneration method and substrate processing device
CN109071104A (en) * 2016-03-31 2018-12-21 富士胶片株式会社 The manufacturing method of semiconductors manufacture treatment fluid, the accepting container for containing semiconductors manufacture treatment fluid, pattern forming method and electronic device
US11693321B2 (en) 2016-03-31 2023-07-04 Fujifilm Corporation Treatment liquid for manufacturing semiconductor, storage container storing treatment liquid for manufacturing semiconductor, pattern forming method, and method of manufacturing electronic device
CN108428645A (en) * 2017-02-15 2018-08-21 东京毅力科创株式会社 substrate liquid processing device
CN108428645B (en) * 2017-02-15 2023-04-07 东京毅力科创株式会社 Substrate liquid processing apparatus
CN111415883A (en) * 2019-01-08 2020-07-14 东京毅力科创株式会社 Substrate processing apparatus, substrate processing method, and storage medium
CN111415883B (en) * 2019-01-08 2024-04-02 东京毅力科创株式会社 Substrate processing apparatus, substrate processing method, and storage medium
CN117344309A (en) * 2023-12-05 2024-01-05 苏州芯慧联半导体科技有限公司 Metal etching liquid recovery control system and control method
CN117344309B (en) * 2023-12-05 2024-03-01 苏州芯慧联半导体科技有限公司 Metal etching liquid recovery control system and control method

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