CN101452224B - Recovery system for tetramethylammonium hydroxide developing solution and method thereof - Google Patents
Recovery system for tetramethylammonium hydroxide developing solution and method thereof Download PDFInfo
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- CN101452224B CN101452224B CN2009100023835A CN200910002383A CN101452224B CN 101452224 B CN101452224 B CN 101452224B CN 2009100023835 A CN2009100023835 A CN 2009100023835A CN 200910002383 A CN200910002383 A CN 200910002383A CN 101452224 B CN101452224 B CN 101452224B
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Abstract
The invention provides a reclaiming method for a tetramethylammonium hydroxide (TMAH) developer. The method comprises the following steps: determining the absorbance of reclaiming liquid respectively as A1 and A2 at the wavelength of 210nm and 220nm; calculating the absorbance (A3) of the developer in the reclaiming liquid to be equal to A1-A2*Co, wherein Co is equal to (A1'-A3')/A2', A1' and A2'are the light absorbance of the tetramethylammonium hydroxide reclaiming liquid at the wavelength of 210nm and 220nm respectively, and A3'is the standard light absorbance of the tetramethylammonium hydroxide reclaiming liquid at the wavelength of 210nm; working out the concentration corresponding to the tetramethylammonium hydroxide light absorbance value A3 according to the standard concentration light absorbance curve of tetramethylammonium hydroxide at the wavelength of 210nm; and according to the concentration value of the tetramethylammonium hydroxide in the reclaiming liquid, adding a proper amount of tetramethylammonium hydroxide till reaching a standard concentration value of the tetramethylammonium hydroxide. The invention also comprises a reclaiming system for the tetramethylammonium hydroxide developer.
Description
It is on 06 27th, 2003 that the present patent application is based on the applying date, and application number is 03148411.5, and denomination of invention is divided an application for the patented claim of " recovery system of tetramethylammonium hydroxide developer solution and method thereof ".
Technical field
The present invention relates to the recovery system of semiconductor factory, particularly the recovery system and the method for tetramethylammonium hydroxide (TMAH) developer solution.
Background technology
General micro-photographing process relates generally to the exposure and the development step of photoresist layer.When photoresist layer after little shadow shifts pattern via light shield, then utilize alkaline-based developer and organic acidity photoresist layer to form the acid-base neutralization reaction and dissolve through exposure, stay photoresist layer structure without exposure.(tetra-methyl-ammonia hydroxide TMAH) then is one of common alkaline-based developer to the organic base tetramethylammonium hydroxide.
And for manufacturing plant; because after the development step, in its relief liquor still based on alkaline developer, for all considerations such as environmental protection and costs; usually can design suitable recovery system, with developer tetramethylammonium hydroxide (hereinafter to be referred as the TMAH) recycling of developing process discharging.The recovery system of known TMAH developer solution, usually utilize the TMAH concentration in electrical conductivity meter (conductivity meter) or ultraviolet light-visible spectrophotometer (UV-visible spectrometer) the mensuration development recovery liquid, and according to the concentration judgement of being measured, with suitable interpolation high concentration TMAH, TMAH in the calibration solution reaches certain alkaline concentration, as the developer solution in the next group development step.If the TMAH concentration of measuring is crossed when hanging down, decidable does not enter the developer solution recovery system yet, and directly is disposed to factory's affair liquid waste system.
Therefore, for the developer solution recovery system, whether the concentration determination of TMAH is accurate, directly influences the quality of developer solution.Yet the mensuration of TMAH often is subjected to reclaiming the interference of other ion in the liquid, formed material behind photoresist and the developer acid-base neutralization for example, and they still can trace dissociate and produce OR
1 -, OR
2 -Or (CH
3)
4NOR
+Plasma, and processing procedure metal remained ion A l
3+, Mo
2+, K
+Or Na
+Deng also may be when developing, dissolve in developer solution and form and disturb.Be decided to be example with known electrical conductivity instrumentation, when the actual electrical conductivity of the TMAH in reclaiming liquid was a%, the measured value of electrical conductivity meter was b%.And form interference owing to have other ion to exist in the recovery liquid, make TMAH electrical conductivity measured value b% greater than actual value a%.That is the TMAH concentration that reclaims in the liquid will be over-evaluated, and makes follow-up correction TMAH concentration that deviation also take place thereupon, makes that the developer solution alkalescence after proofreading and correct is lower than default value.
In addition, (UV-Vis spectrometer) is example with known ultraviolet light-visible spectrophotometer, when desire is measured the TMAH light absorption value that reclaims liquid, can be subjected to reclaiming the light absorption value influence of the photoresist in the liquid, makes that the actual light absorption value of mensuration light absorption value is higher.Therefore directly when reclaiming the liquid absorbance and adjust TMAH concentration, also make and adjust the back to reclaim in the liquid TMAH concentration on the low side.
No matter be mensuration modes such as known electrical conductivity meter or ultraviolet light-visible spectrophotometer, all can't get rid of the interference of reclaiming other ion in the liquid, make that the TMAH concentration of measuring is over-evaluated, have a strong impact on the reliability of proofreading and correct solution level, make the quality of developing process reduce.
Therefore, in known technology, also the someone attempts that (IonChromatography IC), reclaims TMAH in the liquid with ion chromatography tubing string separation determination, and measures its concentration with the high ion chromatograph of precision.Its advantage is by the ion chromatography tubing string, can get rid of the interference of reclaiming other ion in the liquid, can measure the actual value that obtains TMAH concentration.Yet its shortcoming only for carrying out a batch analysis, is analyzed (in-line analysis) for the needed long-time continuous real-time online of developer solution recovery system also because ion chromatograph (IC) belongs to the laboratory-scale analytical instrument, still can't be suitable for.And the ion chromatograph price is high, and consumptive material expense and maintenance cost are all high, and is not suitable for the developer solution recovery system use that general factory is engaged in.
Summary of the invention
In order to address the above problem, one object of the present invention be to provide a kind of fast, economical and the recovery system of tetramethylammonium hydroxide developer solution and method thereof accurately, estimate the concentration that reclaims the tetramethylammonium hydroxide (TMAH) in the liquid exactly with low cost, reclaim the stability of solution level with control.
Recovery method according to a kind of tetramethylammonium hydroxide provided by the present invention (TMAH) developer solution, recovery applicable to tetramethylammonium hydroxide in the recovery liquid after the developing process is used, comprise the following step: select m wavelength between wavelength 220nm to 250nm, wherein m is the positive integer more than or equal to 2; Measure and reclaim the absorbance log of liquid, be respectively Y1 to Ym, and measure and reclaim the absorbance log A1 of liquid at wavelength 210nm at this m set wavelength; Bring this m absorbance log and its corresponding wavelength into polynomial of degree n, in the hope of corresponding wavelength-absorption curve [Y=C
1X
n+ ...+C
nX+C
N+1], wherein X is that wavelength, n are positive integer C
1～C
N+1Be curve coefficients; Bring wavelength 210nm into this wavelength-absorption curve with degree of being absorbed Y
210Calculate A1 and Y
210Difference, obtain reclaiming the tetramethylammonium hydroxide light absorption value A3 in the liquid; Obtain the concentration of this tetramethylammonium hydroxide with tetramethylammonium hydroxide in the normal concentration absorption curve of 210nm in light absorption value A3 correspondence; According to reclaim tetramethylammonium hydroxide concentration value in the liquid add an amount of tetramethylammonium hydroxide with the concentration value that reaches the standard tetramethylammonium hydroxide till; And, this recovery liquid after proofreading and correct is carried out developing process.
According to the present invention, said method further can be used for a kind of recovery system of tetramethylammonium hydroxide developer solution, its recovery that is applicable to tetramethylammonium hydroxide in the developing process recovery liquid is afterwards used, and comprising: accumulator tank, reclaim the recovery liquid of developing machine platform discharging by this reclaim line; Regulating tank in order to the tetramethylammonium hydroxide developer solution of splendid attire high concentration, and is linked to this accumulator tank to regulate pipeline; Spectrophotometer is in order to measure the light absorption value that reclaims liquid in the accumulator tank; Treating apparatus, link this spectrophotometer, in order to calculate the concentration of tetramethylammonium hydroxide in this recovery liquid according to the light absorption value of measuring, and control the pipeline of this regulating tank according to this concentration, to carry an amount of high concentration tetramethylammonium hydroxide developer solution to this accumulator tank, make the tetramethylammonium hydroxide solution level in this accumulator tank reach standard value.And this treating apparatus is tried to achieve the tetramethylphosphonihydroxide hydroxide ammonium concentration according to said method: read the absorbance log Y1 to Ym that reclaims the m of liquid between wavelength 220nm to a 250nm wavelength earlier, and read the absorbance log A1 of recovery liquid at wavelength 210nm; Then, bring m absorbance log and its corresponding wavelength into polynomial of degree n, in the hope of wavelength-absorption curve [Y=C
1X
n+ ...+C
nX+C
N+1]; Then bring wavelength 210nm into this wavelength-absorption curve with degree of being absorbed Y
210Calculate A1 and Y
210Difference, obtain reclaiming the tetramethylammonium hydroxide light absorption value A3 in the liquid; At last, obtain the concentration of this tetramethylammonium hydroxide light absorption value A3 correspondence in the normal concentration absorption curve of 210nm with tetramethylammonium hydroxide.
When the developer solution recovery system is in steady state (SS), the present invention further provides a kind of recovery method of tetramethylammonium hydroxide developer solution of simplification, this method is applicable to the recovery use of tetramethylammonium hydroxide in the developing process recovery liquid afterwards, comprises the following step: measure this recovery liquid and be respectively A1 and A2 in the absorbance log of wavelength 210nm and 220nm; Calculate this developer absorbance log (A3)=A1-A2 * Co in this recovery liquid, wherein, Co=(A1 '-A3 ')/A2 ', A1 ' and A2 ' are respectively the absorbance of the recovery liquid of known tetramethylphosphonihydroxide hydroxide ammonium concentration at 210nm and 220nm, and the A3 ' known tetramethylphosphonihydroxide hydroxide ammonium concentration that is this is at the standard absorbance of 210nm; Obtain the concentration of this tetramethylammonium hydroxide light absorption value A3 correspondence in the normal concentration absorption curve of 210nm with tetramethylammonium hydroxide; Till adding an amount of tetramethylammonium hydroxide and reach standard tetramethylammonium hydroxide concentration value according to the tetramethylammonium hydroxide concentration value in this recovery liquid; And, carry out developing process with this recovery liquid.
Recovery method according to the above-mentioned tetramethylammonium hydroxide developer solution that should simplify, the recovery system of above-mentioned tetramethylammonium hydroxide developer solution, its treating apparatus also can calculate the tetramethylphosphonihydroxide hydroxide ammonium concentration according to this method: at first read the absorbance log of this recovery liquid at wavelength 210nm and 220nm, be A1 and A2; Then calculate this developer absorbance log (A3)=A1-A2 * Co in this recovery liquid, wherein, Co=(A1 '-A3 ')/A2 ', A1 ' and A2 ' are respectively the absorbance of the recovery liquid of known tetramethylphosphonihydroxide hydroxide ammonium concentration at 210nm and 220nm, and the A3 ' known tetramethylphosphonihydroxide hydroxide ammonium concentration that is this is at the standard absorbance of 210nm; At last, obtain the concentration of this tetramethylammonium hydroxide light absorption value A3 correspondence in the normal concentration absorption curve of 210nm with tetramethylammonium hydroxide.
The recovery system and the method for the tetramethylammonium hydroxide developer solution by the invention described above, its advantage is to utilize the spectrophotometer that price is low, stability is high, with treating apparatus, as main frame, can fast detecting and calculate the correct concentration of tetramethylammonium hydroxide in the accumulator tank, can improve developer solution and reclaim the quality of using.
For allow above-mentioned purpose of the present invention, feature, and advantage can become apparent, below cooperate appended graphicly, be described in detail as follows:
Description of drawings
Fig. 1 is tetramethylammonium hydroxide developer solution and the extinction collection of illustrative plates that reclaims liquid.
Fig. 2 is tetramethylammonium hydroxide (TMAH) developer solution and reclaims the extinction collection of illustrative plates of liquid between 200nm to 230nm.
Fig. 3 is the recovery method flow process of the tetramethylammonium hydroxide developer solution in one embodiment of the invention.
Fig. 4 is tetramethylammonium hydroxide developer solution and the absorption collection of illustrative plates that reclaims liquid.
Fig. 5 is the recovery method flow process of the tetramethylammonium hydroxide developer solution in the another embodiment of the present invention.
Fig. 6 is the recovery system frame diagram of the tetramethylammonium hydroxide developer solution in one embodiment of the invention.
Symbol description
The A:TMAH absorption curve, B: reclaim the liquid absorption curve, A1: the absorbance log that reclaims liquid 210nm, A2: reclaim liquid 220nm absorbance log, A3:TMAH is in the 210nm absorbance log, S302～S310: process step, S502～S516: process step, 600: developing machine platform, 602: the waste liquid pipeline, 604: waste liquid tank, 606: transfer valve, 610: reclaim line, 612: accumulator tank, 620: spectrophotometer, 622: diluter, 624: main frame, the 630:TMAH regulating tank, 632: control valve, 634: regulate pipeline, the new liquid bath of 640:TMAH, 642: new liquid pipeline, 644: new fluid valve.
Embodiment
Embodiment 1
Referring to Fig. 1, it is tetramethylammonium hydroxide (TMAH) developer solution and the spectral absorption of reclaiming liquid.Among Fig. 1, curve A is the extinction collection of illustrative plates of TMAH standard solution between 190nm to 300nm, and curve B then is the absorption collection of illustrative plates that liquid is reclaimed in the development of general developing machine platform discharging, reclaims in the liquid and mainly contains TMAH and other interfering material.By among Fig. 1 as can be seen, the TMAH standard solution has not then had absorption near wavelength 225nm; And, become constant amplitude to rise between both approximately at wavelength 225nm to 200nm.Owing to except TMAH, still comprise other interfering material in the recovery liquid,, therefore reclaim the light absorption value of liquid curve B all greater than curve A as photoresistance ion or metallic impurity.
Then referring to Fig. 2, it is tetramethylammonium hydroxide (TMAH) developer solution and reclaims the extinction collection of illustrative plates of liquid between 200nm to 230nm.By among Fig. 2 as can be seen, several TMAH normal concentrations 2.08%, 2.15%, 2.24% and 2.36% o'clock, its absorption curve A and the absorption curve B that reclaims liquid proportional constant amplitude in this wavelength coverage rose.And the TMAH standard solution has not had absorption about 220nm, but the recovery liquid B that contains other ions such as photoresistance then still has absorption curve during greater than 220nm at wavelength.
According to TMAH standard solution among Fig. 1 and Fig. 2 and the extinction figure spectral property that reclaims liquid, be the recovery method that example describes the tetramethylammonium hydroxide developer solution among one of the present invention embodiment in detail below with Fig. 3.
As can be seen from Figure 2, when the stable running of development recovery system, generally speaking, reclaim liquid and standard TMAH solution and between the absorption collection of illustrative plates between wavelength 210nm and 220nm, be set proportionate relationship.Therefore, the present invention is then by finding out curve ratio Co between the two in advance, to calculate the TMAH concentration that reclaims in the liquid.Referring to Fig. 3, at first carry out step S302: calculate the Co value.
Co＝(A1′-A3′)/(A2′-A4′)
Wherein, referring to Fig. 2, A1 ' and A2 ' are respectively the absorbance of the recovery liquid of known tetramethylphosphonihydroxide hydroxide ammonium concentration at 210nm and 220nm, and A3 ' is the standard absorbance of this known tetramethylphosphonihydroxide hydroxide ammonium concentration at 210nm and 220nm with A4 '.As shown in Figure 2, owing to the absorption value of tetramethylammonium hydroxide at 220nm is zero or goes to zero, so A4 ' can omit.
In order to try to achieve Co, can set up the TMAH of tetramethylammonium hydroxide when wavelength 210nm in advance
210Concentration-absorption curve, as inspection amount line, that is when different TMAH concentration, in the corresponding absorbance log of wavelength 210nm.Then get one and reclaim the liquid sample, measure the absorbance of this sample, be respectively A1 ' and A2 ', use analytical instrument again,, analyze the actual content of TMAH in this sample, and this content is contrasted the TMAH that sets up in advance as ion chromatograph (IC) at 210nm and 220nm
210Concentration-absorption curve obtains reclaiming the light absorption value A3 ' of the TMAH in the liquid sample.A1 ', A2 ' according to above-mentioned gained then can calculate the Co value with A3 '.
Then, after obtaining the Co value, carry out step S304: measure and reclaim the absorbance log of liquid, be respectively A1 and A2 at wavelength 210nm and 220nm referring to Fig. 3.Utilize recovery liquid in the spectrophotometer measurement accumulator tank in the absorbance log of these two wavelength, and if its absorbance log greater than 1.2 o'clock, then will reclaim liquid earlier suitably dilutes, and measures absorbance log more again.
Then carry out step S306: the TMAH absorbance log A3=A1-in the calculating recovery liquid (A2 * Co).Referring to Fig. 2, as can be seen from Figure, when recovery system is in steady state (SS), when wavelength 210nm, reclaim the absorbance log difference (A1-A3) of liquid and TMAH titer, become to stablize ratio, i.e. Co with recovery liquid 220nm absorbance log (A2).Therefore, be under the known situation, can extrapolate A3, be the light absorption value that reclaims TMAH in the liquid at A1, A2 and Co.
Then carry out step S308: the concentration of obtaining this tetramethylammonium hydroxide light absorption value A3 correspondence with tetramethylammonium hydroxide in the normal concentration absorption curve of 210nm.The TMAH that can be set up when obtaining Co among the A3 substitution step S302
210Concentration-absorption curve can be tried to achieve corresponding concentration.If reclaiming the absorbance log of liquid is the diluter, then need be scaled the preceding concentration of dilution.
Then carry out step S310: add an amount of tetramethylammonium hydroxide with till reaching standard tetramethylammonium hydroxide concentration value according to reclaiming tetramethylammonium hydroxide concentration value in the liquid.By above-mentioned steps, can calculate and reclaim TMAH concentration actual in the liquid.Because the consumption of developing process, the TMAH concentration that reclaims in the liquid is usually less than standard value, therefore, can accurately adjust the TMAH concentration that reclaims in the liquid, by adding an amount of high concentration TMAH solution, the TMAH that reclaims in the liquid is adjusted to the required normal concentration of developing process, generally be about 2.36%.
At last, carry out step S312: carry out developing process with adjusted recovery liquid.
When TMAH developer solution recovery system is in steady state (SS), can be by the way, the TMAH that sets up variable concentrations earlier measures line in the absorbance of 210nm correspondence as inspection, and the recovery liquid detection product of getting are calculated the Co value in advance, only need afterwards when each the recovery, reclaim the absorbance of liquid when 210nm and the 220nm with spectrophotometer measurement, can extrapolate the TMAH concentration that reclaims in the liquid, with its adjustment TMAH concentration.
Embodiment 2
For the TMAH concentration in the liquid of estimation recovery more accurately, the recovery method flow process of tetramethylammonium hydroxide developer solution in the another embodiment of the present invention is described with Fig. 5 below.
At first referring to Fig. 4, the absorption curve A of TMAH titer does not then have absorption value after wavelength 220nm, and the absorption curve B that therefore reclaims liquid as can be seen greater than the absorption value 220nm after, is other interfering material that comes from the recovery liquid, as photoresist at wavelength.Therefore, method of the present invention is by the absorption curve of foundation recovery liquid greater than 220nm, and in the extrapolation mode, the absorbance log of recovery liquid when reckoning does not contain TMAH again with this anti-absorbance log that reclaims TMAH in the liquid of extrapolating, and then is obtained its concentration.
Detailed step at first carries out step S502 referring to Fig. 5: select m wavelength between wavelength 220nm to 250nm, wherein m is the positive integer more than or equal to 2.Preferably between 220 to 250nm, choose m wavelength with interval 5nm or 10nm, as, seven wavelength such as 220nm, 225nm, 230nm, 235nm, 240nm, 245nm, 250nm selected.According to the present invention, because TMAH does not have absorption behind wavelength 220nm, and consider simultaneously that at wavelength the interference component absorbance log that reclaims in the liquid has not had marked change during greater than 250nm, therefore can represent the trend that reclaims the interference component absorption curve in the liquid with the absorption curve of wavelength 220nm to 250nm.
Then, carry out step S504: measure to reclaim the absorbance log of liquid, and, be respectively Y1 to Ym and A1 in the absorbance log of wavelength 210nm at m set wavelength.If the absorbance log that its 210nm measures then can remeasure its absorbance log through suitable dilution again greater than 1.2 o'clock.
Secondly, carry out step S506: bring m absorbance log and its corresponding wavelength into polynomial of degree n, in the hope of wavelength-absorption curve [Y=C
1X
n+ ...+C
nX+C
N+1].The selection of polynomial of degree n can be decided according to m set wavelength, preferably adopts 3 order polynomials: Y=C
1X
3+ C
2X
2+ C
3X+C
4Above-mentioned 220nm, 225nm, 230nm, 235nm, absorbance log that seven wavelength such as 240nm, 245nm and 250nm etc. are corresponding with it can be brought in 3 order polynomials, obtain coefficient C
1To C
4, obtain reclaiming the wavelength-absorption curve of interfering material in the liquid.
Then, carry out step S508: bring wavelength 210nm into this wavelength-absorption curve with degree of being absorbed Y
210Because above-mentioned wavelength-absorption curve representative is reclaimed the absorption curve of the interfering material except that TMAH in the liquid, is therefore brought X=210nm into this formula Y=C
1X
3+ C
2X
2+ C
3X+C
4In, can try to achieve the absorbance log Y that reclaims interfering material in the liquid
210
Then, carry out step S510: calculate A1 and Y
210Difference, obtain the light absorption value A3 of the tetramethylammonium hydroxide in this recovery liquid.
Secondly, carry out step S512: the concentration of obtaining this tetramethylammonium hydroxide light absorption value A3 correspondence with tetramethylammonium hydroxide in the normal concentration absorption curve of 210nm.If reclaiming the absorbance log of liquid is the diluter, then need be scaled the preceding concentration of dilution.
Then, carry out step S514: according to till reclaiming tetramethylphosphonihydroxide hydroxide ammonium concentration in the liquid and adding an amount of tetramethylammonium hydroxide and reach standard tetramethylammonium hydroxide concentration value.
At last, carry out step S516: the recovery liquid after proofreading and correct is carried out developing process.
According to said method, its TMAH concentration that reclaims liquid is adjusted, only need reclaim liquid after the absorbance log of wavelength 210nm, 220nm, 225nm, 230nm, 235nm, 240nm, 245nm and 250nm by measuring, can push away to such an extent that reclaim TMAH content in the liquid according to above-mentioned steps, to reclaim liquid and be adjusted to standard TMAH concentration to add an amount of high concentration TMAH, can carry out developing process again, keep the development quality.
The advantage of said method is, after each mensuration reclaims the absorbance log of liquid, can calculate the interfering material curve between the 220nm to 250nm again, even therefore recovery system is in dynamic change state, still can be by the way, accurately estimate the TMAH content that in the recovery liquid one by one, adjust foundation as solution level.
Embodiment 3
According to the recovery method of the TMAH of the foregoing description 1, describe the recovery system of the tetramethylammonium hydroxide developer solution in one embodiment of the invention below in detail with Fig. 6.
Referring to Fig. 6, according to recovery system of the present invention, can be connected in developing machine platform 600, the developer solution that is discharged with reclaim line 610 supplying developing boards 600 is to accumulator tank 612.The developer solution of developing machine platform 600 dischargings also can be disposed in the waste liquid tank 604 via waste liquid pipeline 602, and not reclaim.Switching between reclaim line and waste liquid pipeline can be via valve 606 controls.
According to recovery system of the present invention, comprise regulating tank 630, store the TMAH developer solution of high concentration, the TMAH developer solution as 25%, and via regulating pipeline 634 and accumulator tank 612 bindings.Regulate 634 of pipelines and pass through by-pass valve control 632 controls, with the recovery liquid concentration in the developer solution adjustment accumulator tank 612 of carrying high concentration.In addition, accumulator tank 612 can further connect new liquid bath 640, via the TMAH developer solution of pipeline 642 transfer criteria concentration, as 2.36%TMAH to accumulator tank 612.If the developer solution of developing machine platform 600 discharging by 602 emptyings of waste liquid pipeline after, then can replenish new normal concentration TMAH developer solution to accumulator tank 612 by new liquid bath 640.
By visible light-ultraviolet light spectrophotometer (UV-Vis spectrometer) 620, can measure recovery liquid in the accumulator tank 612 in the absorbance log of set wavelength.Preferred spectrophotometer 620 can link a diluter 622, when absorbance log greater than 1.2 the time, then suitably dilute testing sample after, remeasure its absorbance log again.
The measured value of spectrophotometer 620 then is sent to treating apparatus, handles as main frame 624, reclaims TMAH concentration in the liquid to calculate.Main frame 624 can adopt the recovery method among the embodiment 1, preestablishes Co value and the TMAH absorbance inspection amount line when wavelength 210nm.Obtain according to the recovery liquid absorbance log of spectrophotometer 620 at wavelength 210nm and 220nm when main frame 324, A1 and A2 then calculate the method according to embodiment 1, obtain reclaiming (the A2 * Co) of TMAH absorbance log A3=A1-in the liquid.Then main frame 324 is brought TMAH absorbance log A3 the absorbance inspection amount line of TMAH at wavelength 210nm into, to obtain the TMAH concentration that reclaims in the liquid.If reclaiming the absorbance log of liquid is the diluter, then need be scaled the preceding concentration of dilution.
Every batch of adjusted recovery liquid can be delivered in the developer solution supply tank 650 and store, and uses for developing machine platform 600.
Embodiment 4
According to the recovery method of the TMAH of the foregoing description 2, the present invention can provide the recovery system of another TMAH developer solution.
Referring to the frame diagram of the developer solution recovery system of Fig. 6, main frame 624 can calculate the TMAH concentration that reclaims in the liquid according to the method among the embodiment 2.Main frame 624 reclaims liquid absorbance log value of reading at m the set wavelength of 220nm～250nm according to 620 pairs in spectrophotometer, as seven wavelength values of reading such as 220nm, 225nm, 230nm, 235nm, 240nm, 245nm and 250nm, bring polynomial of degree n into, in 3 order polynomials, try to achieve wavelength-absorption curve [Y=C
1X
n+ ...+C
nX+C
N+1].
After main frame 624 was obtained the TMAH concentration that reclaims in the liquid, then according to reclaiming the liquid total amount, according to the TMAH concentration and the TMAH developer solution normal concentration of regulating tank, calculating need be supplemented to the TMAH liquor capacity (V) in the accumulator tank.And main frame 324 is then opened control valve 632 after trying to achieve adjusted volume V, to accumulator tank 612, makes the TMAH concentration that reclaims in the liquid reach the required standard value of developing process with the high concentration TMAH of delivered volume V, is generally 2.36%.
Tetramethylammonium hydroxide developer solution recovery system and method by the invention described above, its advantage is the mensuration of more known simple spectrophotometer or electrical conductivity meter, can release the TMAH concentration that obtains reclaiming in the liquid more accurately, to reclaiming in the liquid, make its TMAH content reach standard value with the TMAH that adds correct amount.And System and method for of the present invention only needs by install a spectrophotometer and a treating apparatus additional in general TMAH recovery system, as main frame, promptly can reclaim the TMAH developer solution by stable high System and method for by low cost.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limit the present invention; for those of ordinary skills; when not breaking away from the spirit and scope of the present invention; should do a little change and retouching, so protection scope of the present invention is looked the appended claims person of defining and is as the criterion.
Claims (5)
1. the recovery method of a tetramethylammonium hydroxide developer solution comprises the following step:
Measure and reclaim the absorbance log of liquid, be respectively A1 and A2 at wavelength 210nm and 220nm;
Calculate the tetramethylammonium hydroxide absorbance log A3 in this recovery liquid, A3=A1-A2 * Co, wherein, Co=(A1 '-A3 ')/A2 ', A1 ' and A2 ' are respectively the absorbance of the recovery liquid of known tetramethylphosphonihydroxide hydroxide ammonium concentration at wavelength 210nm and 220nm, and the A3 ' known tetramethylphosphonihydroxide hydroxide ammonium concentration that is this is at the standard absorbance of wavelength 210nm;
Obtain this with tetramethylammonium hydroxide in the normal concentration absorption curve of wavelength 210nm
Reclaim in the liquidThe concentration of tetramethylammonium hydroxide absorbance log A3 correspondence; And
Add an amount of tetramethylammonium hydroxide with till reaching standard tetramethylammonium hydroxide concentration value according to the tetramethylammonium hydroxide concentration value in this recovery liquid.
2. the recovery method of tetramethylammonium hydroxide developer solution according to claim 1 wherein further comprises step: when this recovery liquid at the absorbance log A1 of wavelength 210nm greater than 1.2 the time, then should reclaim liquid earlier and suitably dilute;
Redeterminate the absorbance log of this recovery liquid at wavelength 210nm and 220nm.
3. the recovery system of a tetramethylammonium hydroxide developer solution, its recovery that is applicable to tetramethylammonium hydroxide in the recovery liquid after the developing process is used, and comprising:
Accumulator tank reclaims the recovery liquid of developing machine platform discharging by reclaim line;
Regulating tank in order to the tetramethylammonium hydroxide developer solution of splendid attire high concentration, and is linked to this accumulator tank to regulate pipeline;
Spectrophotometer is in order to measure the light absorption value of this recovery liquid in this accumulator tank;
Treating apparatus, link this spectrophotometer, calculate the concentration of tetramethylammonium hydroxide in this recovery liquid according to the light absorption value of measuring, and control the pipeline of this regulating tank according to this concentration, to carry an amount of high concentration tetramethylammonium hydroxide developer solution to this accumulator tank, make the tetramethylammonium hydroxide solution level in this accumulator tank reach standard value;
Wherein, this treating apparatus calculates the concentration of tetramethylammonium hydroxide in this accumulator tank in order to following method:
Read the absorbance log of this recovery liquid, be A1 and A2 at wavelength 210nm and 220nm;
Calculate the tetramethylammonium hydroxide absorbance log A3 in this recovery liquid, A3=A1-A2 * Co, wherein, Co=(A1 '-A3 ')/A2 ', A1 ' and A2 ' are respectively the absorbance of the recovery liquid of known tetramethylphosphonihydroxide hydroxide ammonium concentration at wavelength 210nm and 220nm, and the A3 ' known tetramethylphosphonihydroxide hydroxide ammonium concentration that is this is at the standard absorbance of wavelength 210nm; And
Obtain the concentration of the tetramethylammonium hydroxide absorbance log A3 correspondence in this recovery liquid with tetramethylammonium hydroxide in the normal concentration absorption curve of wavelength 210nm.
4. the recovery system of tetramethylammonium hydroxide developer solution according to claim 3, wherein this treating apparatus is a main frame.
5. the recovery system of tetramethylammonium hydroxide developer solution according to claim 3 wherein further comprises diluter, in order to reclaim when this liquid at the absorbance log A1 of wavelength 210nm greater than 1.2 the time, then should reclaim liquid earlier and suitably dilute, and then measure.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031484115A CN100538530C (en) | 2003-06-27 | 2003-06-27 | The recovery system of tetramethylammonium hydroxide developer solution and method thereof |
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| CNB031484115A Division CN100538530C (en) | 2003-06-27 | 2003-06-27 | The recovery system of tetramethylammonium hydroxide developer solution and method thereof |
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| CN101576720B (en) * | 2009-03-02 | 2011-10-19 | 南京华显高科有限公司 | Device and method for recovering silver in developing solution of plasma flat panel display |
| CN102690206A (en) * | 2011-03-25 | 2012-09-26 | 敏森工程有限公司 | Recovery system and method of tetramethylammonium hydroxide |
| TWI423836B (en) * | 2011-05-27 | 2014-01-21 | Chang Chun Petrochemical Co | Process for recovering and purifying tetraalkyl ammonium hydroxide from waste solution containing the same |
| US10386723B2 (en) * | 2016-03-04 | 2019-08-20 | Taiwan Semiconductor Manufacturing Co., Ltd. | Lithography patterning with flexible solution adjustment |
| CN108803258B (en) * | 2018-05-31 | 2021-04-27 | 深圳市华星光电半导体显示技术有限公司 | Development control system and development control method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223881A (en) * | 1991-08-07 | 1993-06-29 | Hirama Rika Kenkyujio Ltd. | Apparatus for controlling developing solution |
| CN1327888A (en) * | 2000-06-09 | 2001-12-26 | 株式会社平间理化研究所 | Treater for substrate surface |
| JP2002107948A (en) * | 2000-09-27 | 2002-04-10 | Dainippon Printing Co Ltd | Method for estimating alkali concentration of developing solution, and equipment therefor |
| CN1402087A (en) * | 2001-08-16 | 2003-03-12 | 株式会社平间理化研究所 | Alkali processing liquor, method and device for preparing processing liquor, and method and device for supply thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223881A (en) * | 1991-08-07 | 1993-06-29 | Hirama Rika Kenkyujio Ltd. | Apparatus for controlling developing solution |
| CN1327888A (en) * | 2000-06-09 | 2001-12-26 | 株式会社平间理化研究所 | Treater for substrate surface |
| JP2002107948A (en) * | 2000-09-27 | 2002-04-10 | Dainippon Printing Co Ltd | Method for estimating alkali concentration of developing solution, and equipment therefor |
| CN1402087A (en) * | 2001-08-16 | 2003-03-12 | 株式会社平间理化研究所 | Alkali processing liquor, method and device for preparing processing liquor, and method and device for supply thereof |
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| CN1567090A (en) | 2005-01-19 |
| CN100538530C (en) | 2009-09-09 |
| CN101452224A (en) | 2009-06-10 |
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