JP2003190949A - Method for regeneration of photoresist developing waste solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for regeneration of a photoresist developing waste solution, capable of simply removing impurity metals such as Na or K difficult to remove, inexpensively and effectively in the regeneration process for a developing waste solution mainly containing a photoresist and tetraalkylammonium hydroxide (TAAH). <P>SOLUTION: In the regeneration process for the photoresist developing waste solution including a process for bringing the photoresist developing waste solution contacted with a cation exchange resin, the process for bringing the photoresist developing waste solution contacted with the cation exchange resin mainly contains the pohtoresist and TAAH contacted with a TAA type acidic cation exchange resin with a specific surface area of 10 m<SP>2</SP>/g or more to remove alkali metal ions such as Na<SP>+</SP>or K<SP>+</SP>. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to a semiconductor device.
(LSI, etc.), liquid crystal display (LCD), print
Photoresist generated in the manufacturing process of electronic components such as substrates
And tetraalkylammonium hydroxide
In particular, the method for treating a photoresist developing waste liquid
Removal of trace impurities such as Na and K during the regeneration process
To process photoresist development wastewater
About the law. [0002] 2. Description of the Related Art Semiconductor devices, liquid crystal displays,
To manufacture electronic components such as lint substrates,
Apply a negative or positive photoresist coating on the substrate
And irradiate a predetermined portion with light or the like, and then apply
Dissolve and develop more unnecessary photoresist,
After processing such as etching, the insoluble photo on the substrate
The resist film must be stripped. Photoresist
Indicates that the exposed part becomes soluble and the exposed part is insoluble
There is a negative type, and a positive type photoresist developer
Alkaline developers are the mainstream, and negative-type photoresist
Organic solvent-based developer is the mainstream developer
However, some use an alkaline developer. [0003] The above-mentioned alkali developing solution is usually
Tetraalkylammonium fluoride (hereinafter abbreviated as TAAH)
You. )) Is used. Therefore, TAAH water
Solution from the development process using the alkaline developer.
Waste fluids typically include dissolved photoresist and TAA
H is contained. Conventionally, contains photoresist and TAAH
The method of treating photoresist developing waste solution
Concentration by the method of collection by a contractor, evaporation method or reverse osmosis membrane method
Waste disposal method (incineration or contractor collection), activated sludge
And biodegradation. Also, the above
Waste liquid obtained as above or TAAH originally
For highly concentrated developer waste, electrodialysis or electrolysis can be used.
Attempts have been made to concentrate and recover TAAH for reuse.
I have. As described above, the electrodialysis method and the electrolysis method
Attempts have been made to concentrate and recover TAAH for reuse
However, the method of concentration by evaporation or reverse osmosis
Soluble photoresist was concentrated with TAAH
Waste liquid concentrated by the evaporation method or reverse osmosis method must be disposed of
It is the present situation that does not get. Biodegraded by activated sludge
The method is based on the poor biodegradability of TAAH and other organic
Decompose organic components if components are mixed in the waste liquid
Microorganisms that promote the growth of microorganisms and decompose TAAH
Growth becomes inactive. Therefore, biodegradation of TAAH
Poor quality, can only be adapted to low concentrations, large scale
Processing facilities are required. On the other hand, by electrodialysis or electrolysis
The method of concentrating and recovering TAAH and reusing it is a countermeasure against
Best in terms of effective use of resources. However, TA by electrodialysis or electrolysis
In the method of concentrating and recovering AH for reuse, the semiconductor
When used in the device manufacturing process, etc.⁺, K⁺,
Ca ²⁺Cations and other impurities remain
Was a problem. [0007] JP-A-11-190907 discloses H
Form or tetraalkyl ammonium (hereinafter TAA)
Removal of Na, K and Ca by cation exchange resin
The prior art has been disclosed. Also, Japanese Patent Application Laid-Open No. 2000-939
No. 55 discloses that aminophosphoric acid and iminodiacetic acid are exchanged
Photoresist development waste liquid depending on the chelate resin
There is disclosed a technique for removing Al and Fe. Only
And Na⁺, K⁺Removal of alkali metal ions such as
It is not a simple matter, but for recent high integration of semiconductor devices
Accordingly, the recycled developer is used in semiconductor device manufacturing factories, etc.
The impact of these trace impurities on the product.
It is entitled. [0008] SUMMARY OF THE INVENTION Therefore, the present invention
Is a photo that mainly contains photoresist and TAAH
Conventional regenerating treatment method for resist developing waste liquid as described above
Na which could not be sufficiently removed⁺, K⁺Etc. Alkali gold
Removal of trace impurities of group ions by simple and inexpensive method
Of waste photoresist development solution
The purpose is to do. [0009] Means for Solving the Problems The present inventors have proposed the above-mentioned technology.
We have been conducting diligent research to solve the issues. As a result,
In the process of regenerating photoresist development waste, the specific surface
Product 10m²/ G or more of cation exchange resin
And Na⁺, K⁺Efficient alkali metal ions such as
And found that it could be removed
Was. That is, the present invention provides a photoresist developing waste liquid.
Contacting a cation exchange resin with a cation exchange resin
In the method for regenerating waste developer waste, the photoresist
The step of contacting the developing waste liquid with the cation exchange resin
Resist developing waste liquid with specific surface area of 10m²/ G or more
Characterized in that it is a step of contacting the on-exchange resin
This is a method of regenerating a photoresist developing waste liquid. [0011] DETAILED DESCRIPTION OF THE INVENTION In the present invention, a photoresist
Development waste liquid is generated during the manufacturing process of various electronic components.
After developing the photoresist with an alkaline developer,
Waste liquid discharged mainly from photoresist and TAAH
Included as Photoresist development waste liquid is usually
It has an alkaline pH of 12-14,
In the alkaline developer waste, the dist is not carboxylated.
Is dissolved in the form of a salt with TAA ions due to acid groups such as
You. TAAH in the photoresist developing waste liquid is:
An alkali used in a photoresist developer,
Specific examples of TAAH include, for example, tetramethyl hydroxide
Ammonium (hereinafter abbreviated as TMAH), tetrahydroxide
Ethyl ammonium, tetrapropyl ammonium hydroxide
System, tetrabutylammonium hydroxide, methyl hydroxide
Liethylammonium, trimethylethylammonium hydroxide
Ammonium, dimethyldiethylammonium hydroxide, hydroxide
Trimethyl (2-hydroxyethyl) ammonium, water
Triethyl oxide (2-hydroxyethyl) ammonium
Dimethyldi (2-hydroxyethyl) ammonium
Ammonium, diethyldi (2-hydroxyethyl) a
Ammonium, methyl trihydroxide (2-hydroxyethyl
) Ammonium, ethyl hydroxide tri (2-hydroxy
Ethyl) ammonium, tetra (2-hydroxy) hydroxide
Ethyl) ammonium and the like. TAAH in the photoresist developing waste liquid is:
As described above, hydroxide ions are partially
Substituted with an anion based on the acid group of dist to form a salt
But, in some cases, further replaced with anions from impurities
TAA salt may be present. In the present invention, photoresist development waste
10m specific surface area²/ G or more of cation exchange resin
Touch. Photoreceptor for contact with cation exchange resin
Photoresist concentration, TAAH concentration
The degree is not particularly limited, and the discharged waste liquid is used as it is.
Alternatively, a concentrated waste liquid may be used. Resin life
The lower the photoresist concentration, the better
The higher the TAAH concentration, the better
No. Prior to contacting with the cation exchange resin
To reduce the organic load of the cation exchange resin
And then neutralize the photoresist developing waste solution with acid to make it insoluble
It is preferable to remove the removed photoresist by filtration.
No. By removing the photoresist,
Reduce the load on equipment and extend the life of cation exchange resin
Can be In this case, the hydroxide ion of TAAH is
TAA is replaced by another anion derived from acid, and TAA is replaced by another anion derived from acid.
The present invention is an alkaline developing method.
Suitable for waste liquids and development waste liquids in which TAA is converted to salts by neutralization
I can respond. The acid used for neutralization is not particularly limited.
Use inorganic acids such as carbonic acid and hydrochloric acid and organic acids such as formic acid and acetic acid
be able to. Easy control of neutralization, waste liquid volume due to neutralization
Carbon dioxide (carbon dioxide) is preferred because the increase in
New In addition to the above neutralization treatment,
As described above, hydroxide ions of TAAH in the developing waste liquid are not
Replaced by other anions derived from pure substances to form TAA salts
It can be. As other anions, for example,
Fluoride ion, chloride ion, bromide ion, carbonate ion
ON, hydrogen carbonate ion, sulfate ion, hydrogen sulfate ion,
Nitrate ion, phosphate ion, hydrogen phosphate ion, phosphoric acid
Inorganic anions such as dihydrogen ion, and formate ion, vinegar
Organic anions such as acid ions and oxalate ions
Can be. Carbonate and bicarbonate ions neutralize
Carbon dioxide gas in the air dissolves into the waste developer
Often present in small amounts. The hydroxylation of TAAH is carried out by neutralization or the like.
If the product ion is replaced by another anion,
When reusing as a liquid, use electrodialysis, electrolysis, etc.
Converts other anions to hydroxide ions to form TAAH
Must be provided during the regeneration process. Electric
Turn other anions into hydroxide ions by electrodialysis, electrolysis, etc.
The process of converting to TAAH is the waste of photoresist development
Install before or after contacting the liquid with the cation exchange resin.
Although it may be provided, it should be installed in front of the organic material load of the resin.
Is preferred. Furthermore, electrodialysis, electrolysis, etc.
Convert anions to hydroxide ions to make TAAH
Before development, develop photoresist with adsorbent such as activated carbon
It is preferable to provide a process for removing COD from waste liquid.
No. Cation exchange resin used in the present invention
Has a specific surface area of 10m²/ G or more cation exchange resin
Available, 20-50m²/ G range of cation exchange resin
Preferably, there is. Specific surface area is 10m²/ G
Then, Na⁺, K⁺Alkali metal ions such as
I can't. The ion exchange group of the cation exchange resin is particularly restricted.
Strongly acidic cation whose exchange group is a sulfonic acid group
Even exchange resins have weak acidic cation exchange
Exchange resin may be used.
Strongly acidic cation exchange resins having acid groups are preferred. example
For example, strong acid cation exchange resin manufactured by Rohm & Haas
Amber List 15DRY, Amber List 35WET
And the like. The counter ion of the cation exchange resin is water
Elementary ions or TAA ions are preferred. Especially counter ion
TAA-type cation exchange resin with TAA ion
In the early stage of passing through the on-exchange resin, TAA ions are positive.
It is adsorbed on the ion exchange resin and its concentration in
More preferable because it can prevent the phenomenon of temporal decline
No. Cation exchange resins are usually commercially available in H or Na form.
These cation exchange resins are used prior to use.
Therefore, it is made into TAA form in advance by TAAH. However,
Not all TAA-type cation exchange resins, but some H-forms
And H-type cation exchange resin
TAA type cation exchange resin can be mixed at any ratio or
They may be used by being laminated. The photoresist developing waste solution is converted to a cation exchange tree.
The method of contacting with fat can be either fixed bed type or moving bed type.
No. Further, the direction of the flow may be an upward flow or a downward flow.
In terms of removing impurities, the chelating resin is replaced with a cation exchange resin.
It is preferable to use in combination with a fat,
Can be used before or after treatment with cation exchange resin
In addition, the cation exchange resin and the chelate resin
Bed) or mixed bed. Chelate
By using in combination with resin, Al³⁺, Fe
²⁺, Fe³⁺And other metal cations
You. Na⁺, K⁺Alkali metal ions such as
Usually, it can be easily removed with a cation exchange resin.
However, it is necessary to adsorb and remove specific ion species from the solution.
Is a major issue in selectivity with other coexisting ion species.
come. In this photoresist developing waste liquid system, it is removed.
Na⁺, K⁺TAA ion in addition to alkali metal ion such as
Contains large amounts of Generally, the odor of cation exchange resin
TAA ions are more selective than Na ions
To remove Na from photoresist development waste⁺, K⁺Al
It is difficult to remove potassium metal ions. However, high specific surface area cation exchange
For resin, the reason is not clear, but TAA ion
Reversal of the selectivity of Na and Na ions,
Na from resist development waste⁺, K⁺Alkali metal ion such as
It is considered that the gas can be sufficiently removed. The photoresist developing waste liquid is treated to obtain N
a⁺, K⁺Removal ability of alkali metal ions such as
By regenerating the cation exchange resin,
The ability to remove alkali metal ions can be restored
You. In the regeneration treatment, the cation exchange resin is converted to an acid such as hydrochloric acid.
To remove the adsorbed Na and K, and then ultrapure water
Wash off excess acid with. In this way, the resin becomes H-shaped
And reuse. As mentioned above, TAAH etc.
Treated with alkali and reused as TAA type
preferable. The flow direction of the regenerant such as acid or TAAH
Even if the direction is the same as the flow direction of the photoresist development waste liquid
Orientation may be. In order to perform regeneration efficiently,
Countercurrent flow for regeneration by flowing regenerant in the opposite direction
The raw method is preferred. [0027] The present invention mainly contains photoresist and TAAH.
In the process of regenerating development waste liquid,
TAAH-containing solution derived therefrom and the specific surface area is 10m²/
g of the present invention comprising a step of contacting with a cation exchange resin of
According to the method, N was not sufficiently removed by the conventional method.
Simple, inexpensive and efficient removal of trace impurities such as a and K
can do. Semiconductor devices, liquid crystal displays, pre-
Used in the production of electronic components that dislike impurities, such as printed circuit boards.
Waste photoresist developing solution to obtain a regenerated developing solution
Before use, COD adsorption removal using activated carbon
Combined with the process and the electrolytic process,
Regenerated T that is highly purified so that it can be used as
AAH can be obtained. [0029] EXAMPLES The present invention will be described in more detail with reference to the following examples.
The present invention will be described with reference to Examples and Comparative Examples.
It is not limited. Emitted from liquid crystal display (LCD) factory
Containing photoresist and TMAH
Concentrate the waste developing waste liquid by the evaporation method, and further add carbon dioxide gas.
The waste liquid obtained by filtering the insolubilized photoresist
Sample liquid discharged from semiconductor device (LSI) factory
Photoresist containing damaged photoresist and TMAH
Developing waste liquid was used as a sample liquid. Sample liquid, sample
Table 1 shows the water quality of the liquid. [0031] [Table 1] The ion exchange resin and chelate resin used were as follows:
Prior to use, ultrapure water cleaning, 1N-HCl cleaning, ultrapure
TMA by water washing, 1N-TMAH washing and ultrapure water washing
Prepared in the form. The space velocity SV of the liquid flowing during each washing is 5 (1
/ Hr), and the amount of liquid used in each step is 5 L / L-resin.
is there. The TMAH concentration was measured by ion chromatography.
Fee method, metal concentration is high frequency inductively coupled plasma / mass
The analysis was performed by an analysis (ICP / MS) method. COD is 100 ° C
Consumption by potassium permanganate in Japan (JI
(SK0101). Embodiment 1 Strongly acidic cation exchange resin Amberlyst 15 WET (ratio
Surface area 50m²/ G, from Rohm & Haas) 50m
10 L of the sample solution (200 L
(L / L-resin) at a space velocity SV = 20 (1 / hr).
Liquid. The water quality of the treatment liquid is shown in Table 2. Impurity metal
Na and K are highly removed. Embodiment 2 Strong acidic cation exchange resin Amberlyst 16WET (ratio
35m surface area²/ G, from Rohm & Haas) 50m
10 L of the sample solution (200 L
(L / L-resin) at a space velocity SV = 20 (1 / hr).
Liquid. The water quality of the treatment liquid is shown in Table 2. Impurity metal
Na and K are highly removed. Embodiment 3 Strongly acidic cation exchange resin Amberlyst 35 WET (ratio
45m surface area²/ G, from Rohm & Haas) 50m
10 L of the sample solution (200 L
(L / L-resin) at a space velocity SV = 20 (1 / hr).
Liquid. The water quality of the treatment liquid is shown in Table 2. Impurity metal
Na and K are highly removed. Embodiment 4 Except using 40L (800L / L-resin) of sample liquid
Conducted the same experiment as in Example 1. Displays the water quality of the processing solution
2 is shown. Highly removed impurity metals Na and K
Have been. Embodiment 5 Except using 40L (800L / L-resin) of sample liquid
Conducted the same experiment as in Example 2. Displays the water quality of the processing solution
2 is shown. Highly removed impurity metals Na and K
Have been. Embodiment 6 Except using 40L (800L / L-resin) of sample liquid
Conducted the same experiment as in Example 3. Displays the water quality of the processing solution
2 is shown. Highly removed impurity metals Na and K
Have been. Comparative Example 1 Strongly acidic cation exchange resin A (specific surface area <0.1m^Two/ G,
Sample on a PFA column filled with 50 ml (commercial A product)
10 liters of liquid (200 L / L-resin) with space velocity SV = 2
The solution was passed at 0 (1 / hr). Table 2 shows the water quality of the treatment liquid.
Was. The impurity metals Na and K have not been removed at all.
No. Comparative Example 2 Strongly acidic cation exchange resin B (specific surface area <0.1m^Two/ G,
(Commercially available company B) sample in PFA column packed with 50 ml
10 liters of liquid (200 L / L-resin) with space velocity SV = 2
The solution was passed at 0 (1 / hr). Table 2 shows the water quality of the treatment liquid.
Was. The impurity metals Na and K have not been removed at all.
No. Comparative Example 3 Strong acidic cation exchange resin C (specific surface area <0.1m^Two/ G,
Sample on a PFA column filled with 50 ml (commercial A product)
40 L of liquid (800 L / L-resin) is subjected to space velocity SV = 2
The solution was passed at 0 (1 / hr). Table 2 shows the water quality of the treatment liquid.
Was. The impurity metals Na and K have not been removed at all.
No. [0043] [Table 2]

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Claims (1)

Claims: 1. A method for regenerating a photoresist developing waste solution, comprising the step of contacting a photoresist developing waste solution with a cation exchange resin, wherein the photoresist developing waste solution is contacted with a cation exchange resin. Is a step of contacting the photoresist developing waste liquid with a cation exchange resin having a specific surface area of 10 m ² / g or more.