KR100560380B1 - System And Method For Recycling Developer Solution Containing Tetra-Methyl-Ammonia-HydroxideTMAH - Google Patents

Abstract

A method and system for adjusting TMAH concentrations. If m is equal to or greater than 2, the adsorption values Y1 to Ym of the developing solution regenerated at wavelength m between 220 nm and 250 nm and wavelength 210 nm, and A1, respectively, are measured. X is a wavelength, n is a positive integer, and C ₁ to C _n are n-th order polynomials, Y = C ₁ X ⁿ +. Y1 and Ym are input to + C _n-1 X + C _n . In order to generate the adsorption value Y ₂₁₀ , the wavelength 210 nm is input in the wavelength adsorption relationship. The difference A3 between A1 and Y ₂₁₀ is calculated as the adsorption value of TMAH in the developing solution, and A3 is input to the adsorption correction curve of TMAH at 210 nm to generate the TMAH concentration. TMAH is then added to provide the corresponding TMAH concentration.

Tetra-methyl-ammonia-hydroxide (TMAH), photoresist developing solution, regeneration

Description

System and Method for Recycling Developer Solution Containing Tetra-Methyl-Ammonia-Hydroxide (TMAH)}

The invention will be more fully understood and more and more advantages will become apparent with reference to the accompanying drawings.

1 shows absorption spectra of new and regenerated TMAH developing solutions, respectively, according to the first embodiment of the present invention;

2 shows absorption spectra of fresh and regenerated TMAH developing solutions, respectively, at wavelengths between 200 nm and 230 nm according to the first embodiment of the present invention;

3 is a flowchart of a method for regenerating a TMAH developing solution according to a first embodiment of the present invention;

4 shows the absorption spectra of each of the new and regenerated TMAH developing solutions used in the second embodiment of the present invention;

5 is a flowchart of a method for regenerating a TMAH developing solution according to a second embodiment of the present invention;

6 shows a system structure for regenerating a TMAH developing solution according to the present invention.

The present invention relates to a regeneration system for a semiconductor factory, in particular to a system and method for regenerating a photoresist developing solution comprising tetra-methylammonium hydroxide (TMAH).

In semiconductor fabrication, a photographic plate includes the exposure and development of a photoresist layer overlying a semiconductor substrate to define a pattern thereon. Typically, the exposed organic acid photoresist is neutralized and dissolved in the base developer and the unexposed photoresist pattern remains as a mask. Tetra-methyl-ammonia-hydroxide (TMAH) is widely used as the base photoresist developing solution. Generally, semiconductor factories regenerate and reuse base TMAH development solutions with a regeneration system. Common systems use conductivity meters or UV spectrometers to measure the concentration of TMAH in the regenerated solution. The regenerated solution with the addition of TMAH is then adjusted to a predetermined alkaline level according to the measured concentration. The adjusted TMAH developing solution is used as a photoresist developing solution for a continuous photographic plate. After several regenerations, the regenerated TMAH developing solution is discharged into the waste system.

The quality of the developing solution depends on the concentration of TMAH. However, the concentration of TMAH depends on the ions in the regenerated solution. For _{^{example, OR 1 -, OR 2 -}} , or (CH _{3) 4} remaining on the metal ion neutralized compounds of the photoresist and the developer solution was ionized semiconductor substrate in order to generate a NOR ⁺ Al ^3+, Mo ²⁺ , K ⁺ , or Na ⁺ is rinsed with the developing solution. When a conductivity meter is used, the measured conductivity b% of the regenerated developing solution is higher than the actual conductivity a% due to the regenerated solution containing ions other than the base TMAH. Since the TMAH concentration in the regenerated solution is higher than expected, the alkalinity, ie the TMAH concentration of the adjusted regenerated solution, becomes inaccurate.

When a UV spectrometer is used for TMAH adjustment, the adsorption value of regenerated TMAH is governed by the photoresist resistance in the regenerated solution. The measured adsorption value is higher than the actual adsorption value of TMAH. Likewise, the alkalinity of the adjusted regenerated solution is incorrect.

It is difficult to reduce the effects of other ions in the regenerated solution using a conductivity meter or UV spectrometer. Thus, the accuracy of the continuous photographic plate and the quality of the adjusted TMAH concentration are reduced.

To separate TMAH from the regenerated solution to determine the concentration of other ions, the solution uses high accuracy ion chromatography (IC) to determine the exact concentration of TMAH. The drawback of the IC is that it is laboratory scale and the concentration determination of a series of processes is not suitable for continuous and long-term in-line analysis of the TMAH regeneration system. On the other hand, the cost and maintenance cost of the materials used for ion chromatography are expensive to be used in the TMAH regeneration system.

 It is an object of the present invention to provide a fast, economical and accurate TMAH regeneration system and method for accurately measuring TMAH concentration in regeneration systems so that the alkalinity of TMAH in the regenerated developing solution can be controlled.

The present invention provides a method of adjusting the tetra-methyl-ammonia-hydroxide (TMAH) concentration for regeneration. If m is equal to or greater than 2, the M wavelength is preselected between 220 nm and 250 nm. The adsorption values Y1 to Ym of the developing solution regenerated at a wavelength of 220 nm and a wavelength of 250 nm and a wavelength of 210 nm, and A1 are measured, respectively. In Y1, Ym is a wavelength adsorption relationship Y = C ₁ X ⁿ +... Where X is a wavelength, n is a positive integer, and C ₁ to C _n are relation coefficients. Substitute the nth order polynomial to produce + C _n-1 X + C _n . In order to generate the adsorption value Y ₂₁₀ , the wavelength 210 nm is input in the wavelength adsorption relationship. The difference A3 between A1 and Y ₂₁₀ is calculated as the adsorption value of TMAH in the developing solution, and then A3 is input to the adsorption correction curve of TMAH at 210 nm to generate the corresponding TMAH concentration. Next, TMAH is added to the regenerated developing solution according to the corresponding TMAH concentration.

According to the present invention, there is also provided a regeneration system of a developing solution comprising TMAH. The regeneration system includes a regeneration tank for collecting regenerated developing solution from the photoresist system via the regeneration pipeline. The regulating tank is connected to the regeneration tank via the regulating pipeline for the loading of high concentration TMAH. The spectrometer is connected to the regeneration tank for measuring the adsorption value of the developing solution in the regeneration tank. The processor is connected to the spectrometer and the calibration pipeline, and is programmed to calculate the TMAH concentration in the regeneration tank according to the adsorption values measured from the spectrometer, and adjust the high concentration of TMAH to obtain the desired TMAH concentration according to the calculated TMAH concentration. Transport from the pipeline to the regeneration tank. The processor is programmed to calculate the TMAH concentration in the regeneration tank by the following steps. If m is equal to or greater than 2, the adsorption values of Y1 to Ym at m wavelengths between 220 nm and 250 nm of the regenerated developing solution are read separately and the adsorption values A1 on 210 nm are also read. Next, Y ₁ to Y _m are wavelength adsorption relations Y = C ₁ X ⁿ +... Where X is a wavelength, n is a positive integer, and C ₁ to C _n are relation coefficients. It is entered into the nth order polynomial to generate + C _n-1 X + C _n . In order to generate the adsorption value Y ₂₁₀ , the wavelength 210 nm is input in the wavelength adsorption relationship. The difference A3 between A1 and Y ₂₁₀ is calculated as the adsorption value of TMAH in the developing solution. A3 is entered into the adsorption calibration curve of TMAH at 210 nm to produce the corresponding TMAH concentration in the regeneration tank.

When the regeneration system is stable, the present invention also provides a simple method for regenerating a developing solution comprising tetra methyl ammonia hydroxide (TMAH). Adsorption values A1 and A2 of the regenerated developing solution are measured at wavelengths of 210 nm and 220 nm. Co = (A1'-A3 ') / A2', A1 'and A2' are the adsorption values of the regenerated developing solution of known TMAH concentration at 210 nm and 220 nm, respectively, and A3 'is the standard of known TMAH concentration at 210 nm. In the case of an adsorption value, the adsorption value A3 of TMAH in a developing solution is computed as A3 = A1-A2 * Co. A3 is entered into the adsorption calibration curve of TMAH at 210 nm to produce the corresponding TMAH concentration. TMAH is thus added to the regenerated developing solution, thereby achieving the desired TMAH concentration.

The present invention also provides a processor for use in the regeneration system that is programmed to calculate the TMAH concentration in the regeneration tank according to the following steps. The adsorption values A1 and A2 of the regenerated solution regenerated at wavelengths of 210 nm and 220 nm are read. Co = (A1'-A3 ') / A2', A1 'and A2' are the adsorption values of the regenerated developing solution of known TMAH concentration at 210 nm and 220 nm, respectively, and A3 'is the standard of known TMAH concentration at 210 nm. In the case of an adsorption value, the adsorption value A3 of TMAH in a developing solution is computed as A3 = A1-A2 * Co. A3 is entered into the adsorption calibration curve of TMAH at 210 nm to produce the corresponding TMAH concentration.

According to the present invention, a low cost, high stability spectrometer is used through a processor such as a computer in which the TMAH concentration in the regeneration tank is accurately calculated and adjusted.

DETAILED DESCRIPTION OF THE INVENTION A detailed description of the present invention will be given below with reference to the accompanying drawings.

Without being limited in any way, the present invention will be further described in the following examples.

<First Embodiment>

1 shows adsorption spectra of the fresh and regenerated TMAH developing solutions according to the first embodiment of the present invention, respectively. Curves A and B represent the absorption spectra of each of the fresh and regenerated TMAH developing solutions at wavelengths 190 nm to 300 nm. As shown in FIG. 1, there is no adsorption of the new TMAH solution at a wavelength of 220 nm or higher. The adsorption spectra of new and regenerated TMAH increase proportionally at wavelengths from 225 nm to 200 nm. Adsorption of curve B is larger than curve A because of the influence of ionized photoresist or other ions such as metal ions in the regenerated solution.

Figure 2 shows the absorption spectra of the fresh and regenerated TMAH developing solutions, respectively, at wavelengths between 200 nm and 230 nm according to the first embodiment of the present invention. Part A, the adsorption curve of TMAH, which is new at various concentrations of 2.08%, 2.15%, 2.24% and 2.36%, deviates slightly from each other. There is no adsorption of new TMAH solutions at 220 nm or higher wavelengths. However, regenerated TMAH which still contains other ions at wavelengths larger than 220 nm in the absorption spectrum (part B) is still detected. The adsorption spectra of the new and regenerated TMAH show a proportional decrease between 210 nm and 220 nm even with different TMAH concentrations.

According to the adsorption profile shown in FIGS. 1 and 2, a method for regenerating a TMAH developing solution according to the present invention is provided as in FIG. 3.

When the regeneration system is stable, the adsorption spectra of regenerating and fresh TMAH solutions at 210 nm to 220 nm are proportional as shown in FIG. 2. The TMAH concentration in the regenerated developing solution can be calculated according to the proportional ratio Co of the absorption spectrum of the regenerated developing solution comprising the standard TMAH solution and TMAH. As shown in FIG. 3, the proportional ratio Co of the adsorption spectrum is calculated in step 302, where Co = (A1'-A3 ') / (A2'-A4'.

As shown in Fig. 2, A1 'and A2' are adsorption values of the regenerated developer solution of known TMAH concentration at 210 nm and 220 nm, respectively. A3 'and A4' are adsorption values of standard TMAH solutions of known concentrations at 210 nm and 220 nm, respectively. Since the adsorption of the standard TMAH solution at 220 nm is zero or negligible, A4 'can be omitted as Co = (A1'-A3') / A2 '.

In order to calculate Co, a series of standard TMAH solutions are detected at 210 nm to construct an adsorption correction curve into a TMAH ₂₁₀ concentration adsorption curve, which is the relationship between various standard TMAH concentrations and their corresponding adsorption values. The regenerated solution was detected at 210 nm and 220 nm, respectively, to obtain the corresponding adsorption values A1 'and A2'. In addition, the exact TMAH concentration in the regenerated solution is further detected in analytical instruments or assays such as ion chromatography. The adsorption value A3 'of the exact concentration of TMAH in the regenerated solution can be calculated based on the TMAH ₂₁₀ concentration adsorption calibration curve. Therefore, Co can be calculated according to the adsorption values A1 ', A2' and A3 '.

After Co is calculated, the adsorption values of the targeted regenerated solutions A1 and A2 are measured at 210 nm and 220 nm, respectively, in step S304. A general spectrometer can be used to measure the adsorption of regenerated solution in the regeneration tank. If any detected adsorption value exceeds 1.2, the regenerated solution sample is diluted and measured again.

Adsorption of TMAH A3 in the regenerated solution as follows is calculated in step S306: A3 = A1- (A2 × Co)

As shown in Fig. 2, when the regeneration system is stable, the adsorption difference between the regenerated solution at 210 nm and the TMAH standard solution, (A1-A3), is proportional to the adsorption value of the regenerated solution at 220 nm, A2. Thus, if A1, A2 and Co are known, A3 can be calculated as the adsorption value of TMAH in the regenerated solution.

In step S308, the corresponding concentration of the TMAH adsorption value A3 is calculated based on the standard calibration curve of the TMAH concentration and the adsorption. In the example, A3 is input to the TMAH ₂₁₀ concentration adsorption calibration curve constructed at S302 to calculate the corresponding TMAH concentration. If the adsorption of the regenerated solution is a dilute value, the actual concentration of TMAH in the regenerated solution is reduced according to the dilution ratio.

After the actual concentration of TMAH in the regenerated solution is calculated, the amount of TMAH is added to the regenerated solution to obtain the desired TMAH concentration in step S310. Since TMAH is consumed during the development process, the TMAH concentration in the regenerated solution is usually less than the required TMAH concentration. According to the actual TMAH concentration calculated in this step, the amount of TMAH added for the regenerated solution can be calculated according to the actual TMAH concentration and the volume of the regenerated solution. Preferably, a high concentration of TMAH solution is added to the regenerated solution to adjust to a concentration of approximately 2.36%. Finally, the adjusted regenerated solution is reused for subsequent development.

When the regeneration system of the developing solution is running steadily, this step immediately provides a valid solution to adjust the regenerated TMAH concentration. The standard calibration curve of the series of TMAH solutions is predetermined at 210 nm as the concentration adsorption calibration curve. The regenerated solution is preliminarily sampled and measured to calculate Co. The TMAH concentration in any batch of regenerated solution is then adjusted by measuring the adsorption values of regenerated solution at 210 nm and 220 nm according to the above steps.

Second Embodiment

In order to more accurately measure TMAH concentration in the regenerated solution, Figure 5 shows a method for regenerating a TMAH developing solution according to another embodiment of the present invention.

As shown in FIG. 4, curve A lacks adsorption of TMAH standard solutions at wavelengths of 220 nm or greater. Adsorption of the regenerated solution at 220 nm or above, curve B, is caused by contaminating ions in the regenerated solution, such as ionized photoresist or metal ions. The present invention provides an absorption spectrum of a regenerated solution at a wavelength of 220 nm or more. Adsorption of regenerated solution without TMAH at 210 nm is estimated by extrapolation. Adsorption of TMAH in the regenerated solution is calculated and so their concentration is estimated.

If m is equal to or larger than 2, the M wavelength is selected in advance between 220 nm and 250 nm in step S502. Preferably, the m wavelength is selected at intervals of 5 nm or 10 nm. As shown in Fig. 4, m wavelengths are 220 nm, 225 nm, 230 nm, 235 nm, 240 nm, 245 nm and 250 nm, since there is no adsorption of TMAH at 220 nm or more and the adsorption spectrum of the regenerated solution tends to be flat at 250 nm or more. 7 wavelengths of are selected here. Thus, the adsorption spectrum at 220 nm to 250 nm is a curve showing the tendency of adsorption of contaminating ions in the regenerated solution.

The adsorption values Y1 to Ym of the developing solution regenerated at the m wavelength, and the adsorption values A1 at the wavelength of 210 nm are respectively measured in step S504. If the adsorption measured at 210 nm is greater than 1.2, the developing solution regenerated to obtain A1, Y1 to Ym is diluted and measured again.

Y1 to Ym are wavelength adsorption relations Y = C ₁ X ⁿ +... Where S is a wavelength, n is a positive integer, and C ₁ to C _n are relation coefficients in step S506. It is entered into the nth order polynomial to generate + C _n-1 X + C _n . In order to generate the adsorption value Y ₂₁₀ , the wavelength 210 nm is input in the wavelength adsorption relationship. The nth order is determined by the m wavelength. Preferred nth-order polynomials are 2-5th polynomials. More preferred nth order polynomials are ^third order polynomials such as Y = C ₁ X ³ + C ₂ X ² + C ₃ X + C ₄ . Coefficient to establish a wavelength absorption relationship of contamination ions in the regenerated solution in which C ₁ to wavelength to obtain a _{C n 220nm, 225nm, 230nm,} 235nm, 240nm, 245nm, 250nm , and the absorption value is a third degree polynomial Y = C ₁ Enter X ³ + C ₂ X ² + C ₃ X + C ₄ .

In step S508, the wavelength 210 nm is input in the wavelength adsorption relationship to obtain the adsorption Y ₂₁₀ . Since the wavelength adsorption relationship obtained in step S506 represents the adsorption curve of contaminant ions in the regenerated solution, the adsorption of contaminant ions Y ₂₁₀ is determined by the equation, Y = C ₁ X ³ + C ₂ X ² + C ₃ X + C ₄ . Calculated by substituting X = 210nm.

The difference A3 between A1 and Y ₂₁₀ is calculated as the adsorption value of TMAH in the developing solution in step S510.

In order to generate the corresponding TMAH concentration in the regenerated solution in the next step S512, A3 is input to the adsorption correction curve of TMAH at 210 nm. The adsorption calibration curve of TMAH at 210 nm can be predetermined by measuring the adsorption of a series of concentrations of standard TMAH solution. If the adsorption of the regenerated solution is a diluted value, the actual concentration of TMAH is reduced according to the dilution ratio.

After the actual concentration of TMAH in the regenerated solution is calculated, the amount of TMAH is added to the regenerated solution to obtain the desired TMAH concentration in step S514.

Finally, the adjusted regenerated solution is reused for the continuous development process in step S516.

According to the method, the adjustment of TMAH in the regenerated solution can be obtained by measuring the adsorption of the regenerated solution at 210 nm, 220 nm, 225 nm, 230 nm, 235 nm, 240 nm, 245 nm and 250 nm. The actual concentration of TMAH in the regenerated solution can be calculated according to this step. The TMAH concentration in the regenerated solution can be adjusted to it.

The method can be used in a dynamic playback system. The adsorption value of contaminating ions in the regenerated solution between 220 nm and 250 nm can be measured each time, thus obtaining a revised wavelength adsorption relationship for the TMAH adjustment.

Third Embodiment

The system structure for regenerating the TMAH developing solution of the present invention described in the first embodiment is described in more detail in FIG. 6 which shows the system structure for regenerating the TMAH developing solution of the present invention.

As shown in FIG. 6, the regeneration tank 612 stores the developing solution regenerated from the photoresist developing system 600 through the regeneration pipeline 610. The regenerated developing solution may also be discharged from the discharge pipeline 602 into the waste liquid tank 604. The switch between the regeneration pipeline 610 and the discharge pipeline 602 is controlled by the gate valve 606.

The regeneration system also includes a regulating tank 630 for the loading of high concentrations of TMAH, such as a 25% TMAH solution, and is connected to the regeneration tank 612 with a regulating pipeline 634 for incoming TMAH. Regulating pipeline 634 is controlled by gate valve 632. Preferably, the regeneration tank 612 is connected to a new developing solution tank 640 which introduces a new standard TMAH developing solution, such as 2.36% TMAH, into the regeneration tank 612 via pipeline 642. When the developing solution is drained from the photoresist developing system 600 through the discharge pipeline 602, a new standard TMAH developing solution may be supplied by a new developing solution tank 640.

A UV spectrometer 620 is connected to the regeneration tank 612 to measure the adsorption value of the developing solution in the regeneration tank. Preferably, diluent 622 is connected to a UV spectrometer 620 to dilute the sampled regenerated solution when any adsorption value is greater than 1.2.

A processor, such as a computer 624, is connected with the spectrometer 620 and the adjustment pipeline 632. Computer 624 is programmed according to the method in the first embodiment to calculate the TMAH concentration in the regeneration tank 612. Adsorption correction curves of Co and TMAH at 210 nm are predetermined and stored in computer 624. Once the adsorption value of the regenerated solution at 210 nm and nm A1 and A2 are received on the spectrometer 620, the computer 624 is programmed to calculate the adsorption value of TMAH in the regenerated solution A3 as follows:

A3 = A1- (A2 × Co)

The computer 624 is programmed to input the adsorption value A3 into the adsorption correction curve of TMAH at 210 nm to calculate the concentration of TMAH in the regenerated solution. If the adsorption of the regenerated solution is a diluted value, the actual concentration of TMAH is reduced according to the dilution ratio.

After the TMAH concentration in the regenerated solution is calculated, the computer 624 is programmed to calculate the replenishment volume (V) of the high concentration TMAH for the regeneration tank 612 according to the volume of regenerated solution and the TMAH concentration in the regeneration tank 612. Computer 624 opens gate valve 632 to introduce a high volume of TMAH in volume V into regeneration tank 612, thereby adjusting the TMAH concentration in the regenerated solution to a predetermined concentration, 2.36%.

The adjusted regenerated solution is introduced into feed tank 650 for a continuous photographic plate to the photoresist developing system 600.

Fourth Example

Another system for reproducing TMAH using the reproducing method described in the second embodiment is described based on the system structure shown in FIG.

Computer 624 is programmed according to the method described in the second embodiment to calculate the TMAH concentration in the regeneration tank 612. Computer 624 is programmed to read the adsorption values Y1 to Ym of the developing solution regenerated at m wavelength, and the adsorption value A1 at wavelength 210 nm. Preferably, m is equal to or greater than two. In this example, adsorption values Y1 to Y7 at 220 nm, 225 nm, 230 nm, 235 nm, 240 nm, 245 nm and 250 nm are obtained from the spectrometer 620, X is the wavelength, n is a positive integer, and C ₁ to C _n are the relationships Wavelength adsorption relation Y = C ₁ X ⁿ +. It is entered into the nth order polynomial to generate + C _n-1 X + C _n . In this example, the adsorption values Y1 to Y7 are entered as a third order polynomial, Y = C ₁ X ³ + C ₂ X ² + C ₃ X + C ₄ .

Computer 624 is programmed to input wavelength 210 nm in wavelength adsorption relationship to produce adsorption value Y ₂₁₀ . The difference A3 between A1 and Y ₂₁₀ is calculated as the adsorption value of TMAH in the regenerated solution. The computer 624 is programmed to input A3 into the adsorption correction curve of the TMAH preset at 210 nm to produce the corresponding TMAH concentration in the regeneration tank 612. If the adsorption of the regenerated solution is a diluted value, the actual concentration of TMAH is reduced according to the dilution ratio.

After the TMAH concentration in the regenerated solution is calculated, the computer 624 is programmed to calculate the replenishment volume (V) of the high concentration of TMAH for the regeneration tank 612 according to the volume of regenerated solution and the TMAH concentration in the regeneration tank 612. Computer 624 opens gate valve 632 to introduce a high volume of TMAH in volume V into regeneration tank 612, thereby adjusting the TMAH concentration in the regenerated solution to a predetermined concentration, 2.36%.

The regeneration method and system of the present invention allows the calculation of the correct TMAH concentration in the regenerated solution without the influence of other ions. Thus, the adjustment of TMAH in the regenerated solution is more accurate. Moreover, processors such as spectrometers and computers provide solutions for which TMAH concentrations are measured at a lower cost than expensive ion chromatography.

Although the present invention has been described by the above-mentioned embodiments, the present invention is not limited to the disclosed embodiments. On the other hand, the present invention is intended to cover various modifications and similar arrangements as will be apparent to those skilled in the art. Accordingly, the scope of the following claims should be construed broadly to include all such modifications and similar arrangements.

Claims (18)

m is equal to or greater than 2 and selects the m wavelength between 220 nm and 250 nm; the adsorption values Y1 to Ym of the developing solution regenerated at the m wavelength, and the adsorption values A1 at a wavelength of 210 nm are measured, X is a wavelength, n is a positive integer, and C ₁ to C _n are n-th order polynomials, Y = C ₁ X ⁿ +. Input Y1 and Ym to + C _n-1 X + C _n , In order to generate the adsorption value Y ₂₁₀ , the wavelength 210 nm is input in the wavelength adsorption relation, As absorption value of TMAH in the developing solution, and calculating the difference between A1 and A3 of the Y _210, Input A3 into the adsorption calibration curve of TMAH at 210 nm to produce the corresponding TMAH concentration; A method of regenerating a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH) comprising adding TMAH to a regenerated developing solution according to the corresponding TMAH concentration for reuse. The method of claim 1, M wavelength is selected at intervals of 5 nm or 10 nm. The method of regenerating a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH). The method of claim 2, Said m wavelength is seven wavelengths of 220 nm, 225 nm, 230 nm, 235 nm, 240 nm, 245 nm, and 250 nm, The reproduction method of the photoresist development solution containing tetra-methyl-ammonium hydroxide (TMAH). The method of claim 1, The n-th order polynomial is a second to fifth polynomial, characterized in that the tetra-methyl-ammonia-hydroxide (TMAH) containing photoresist developing solution containing. The method of claim 4, wherein The n-th order polynomial is a tertiary polynomial of Y = C ₁ X ³ + C ₂ X ² + C ₃ X + C ₄ , wherein the photoresist development solution containing tetra-methyl-ammonia-hydroxide (TMAH) is used. How to play. The method of claim 1, Dilute the regenerated developing solution when the adsorption value A1 at a wavelength of 210 nm exceeds 1.2, A method for regenerating a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH), which further comprises re-measuring the adsorption of the regenerated adsorption solution diluted at m wavelength and 210 nm with Y1 to Ym and A1. Measure the adsorption values A1 and A2 of the regenerated developing solution at wavelengths of 210 nm and 220 nm, Co = (A1'-A3 ') / A2', A1 'and A2' are the adsorption values of the regenerated developing solution of known TMAH concentration at 210 nm and 220 nm, respectively, and A3 'is the standard of known TMAH concentration at 210 nm. In the case of the adsorption value, the adsorption value A3 of TMAH in the developing solution is calculated as A3 = A1-A2 × Co, To generate the corresponding TMAH concentration, A3 is entered into the adsorption calibration curve of TMAH at 210 nm, A method of regenerating a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH) comprising adding TMAH to a regenerated developing solution according to the TMAH concentration for reuse. The method of claim 7, wherein Dilute the regenerated developing solution when the adsorption value A1 at a wavelength of 210 nm exceeds 1.2, A method for regenerating a photoresist resistive solution containing tetra-methyl-ammonia-hydroxide (TMAH), which further comprises re-adsorption of the regenerated adsorption solution diluted at 210 nm and 220 nm with A1 and A2. A regeneration tank for collecting regenerated developing solution from the photoresist developing system through a regeneration pipeline; A regulating tank connected to said regenerative tank by a regulating pipeline and for loading a high concentration of TMAH; A spectrometer for measuring the adsorption value of the developing solution in the regeneration tank; Connected to the spectrometer and calibration pipeline, and programmed to calculate the TMAH concentration in the regeneration tank according to the adsorption values measured from the spectrometer, and from the calibration pipeline to the regeneration tank to obtain the desired TMAH concentration according to the calculated TMAH concentration. Carries the amount of TMAH, next stage: when m is equal to or greater than 2, reading the adsorption values Y1 to Ym at m wavelengths between 220 nm and 250 nm of the regenerated solution, and adsorption values A1 at wavelengths 210 nm; X is the wavelength, n is a positive integer, and C ₁ to C _n are the coefficients of the wavelength adsorption relation Y = C ₁ X ⁿ +. Inputting Y1 and Ym into an n th polynomial to produce + C _n-1 X + C _n ; Inputting a wavelength of 210 nm in a wavelength adsorption relationship to produce an adsorption value Y ₂₁₀ ; Calculating a difference A3 between A1 and Y ₂₁₀ as an adsorption value of TMAH in the developing solution; And Inputting A3 to the adsorption calibration curve of TMAH at 210 nm to produce the corresponding TMAH concentration in the regeneration tank; a tetra-methyl-ammonia-hydroxide comprising a processor programmed to calculate the TMAH concentration in the regeneration tank according to Regeneration system of photoresist developing solution containing TMAH). The method of claim 9, And said processor is a computer. The regeneration system of a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH). The method of claim 9, The m wavelength is selected at intervals of 5 nm or 10 nm. Regeneration system of a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH). The method of claim 11, Said m wavelength is seven wavelengths of 220 nm, 225 nm, 230 nm, 235 nm, 240 nm, 245 nm, and 250 nm, The regeneration system of the photoresist developing solution containing tetra-methyl-ammonium hydroxide (TMAH) characterized by the above-mentioned. The method of claim 9, The n-th order polynomial is a second to fifth polynomial, characterized in that the regeneration system of a photo-resist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH). The method of claim 13, The n-th order polynomial is a tertiary polynomial of Y = C ₁ X ³ + C ₂ X ² + C ₃ X + C ₄ , wherein the photoresist development solution containing tetra-methyl-ammonia-hydroxide (TMAH) is used. Regeneration system. The method of claim 9, A regeneration system of a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH), further comprising a diluent diluting the regenerated developing solution when the adsorption value A1 at a wavelength of 210 nm exceeds 1.2. A regeneration tank for collecting regenerated developing solution from the photoresist developing system through a regeneration pipeline; A regulating tank connected to said regenerative tank by a regulating pipeline and for loading a high concentration of TMAH; A spectrometer for measuring the adsorption value of the developing solution in the regeneration tank; Connected to the spectrometer and the calibration pipeline, and programmed to calculate the TMAH concentration in the regeneration tank according to the adsorption values measured from the spectrometer, and from the calibration pipeline to the regeneration tank to obtain the desired TMAH concentration according to the calculated TMAH concentration. Carries the amount of TMAH, next stage: Measuring adsorption values A1 and A2 of the regenerated solution regenerated at wavelengths of 210 nm and 220 nm; Co = (A1'-A3 ') / A2', A1 'and A2' are the adsorption values of the regenerated developing solution of known TMAH concentration at 210 nm and 220 nm, respectively, and A3 'is the standard of known TMAH concentration at 210 nm. When the adsorption value, the adsorption value A3 of TMAH in the developing solution is calculated as A3 = A1-A2 × Co; To generate the corresponding TMAH concentration in the regeneration tank, A3 enters the adsorption calibration curve of the TMAH at 210 nm; a processor programmed to calculate the TMAH concentration in the regeneration tank, according to a tetra-methyl-ammonia-hydroxide (TMAH Regeneration system of a photoresist developing solution containing a). The method of claim 16, And said processor is a computer. The regeneration system of a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH). The method of claim 16, A regeneration system of a photoresist developing solution containing tetra-methyl-ammonia-hydroxide (TMAH), further comprising a diluent diluting the regenerated developing solution when the adsorption value A1 at a wavelength of 210 nm exceeds 1.2.

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