KR101821034B1 - A method of stripping photoresist - Google Patents
A method of stripping photoresist Download PDFInfo
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- KR101821034B1 KR101821034B1 KR1020160017409A KR20160017409A KR101821034B1 KR 101821034 B1 KR101821034 B1 KR 101821034B1 KR 1020160017409 A KR1020160017409 A KR 1020160017409A KR 20160017409 A KR20160017409 A KR 20160017409A KR 101821034 B1 KR101821034 B1 KR 101821034B1
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- Prior art keywords
- substrate
- photoresist
- peeling
- water
- solution
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 64
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- -1 amine compound Chemical class 0.000 claims description 9
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- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
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- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 description 1
- XGIKILRODBEJIL-UHFFFAOYSA-N 1-(ethylamino)ethanol Chemical compound CCNC(C)O XGIKILRODBEJIL-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
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- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/30—Technical effects
- H01L2924/35—Mechanical effects
- H01L2924/351—Thermal stress
- H01L2924/3512—Cracking
- H01L2924/35121—Peeling or delaminating
Landscapes
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
The present invention discloses a photoresist stripping method having high reusability of an aqueous stripper solution.
Description
The present invention relates to a method for peeling photoresist in semiconductor and display manufacturing processes. More particularly, the present invention relates to an eco-friendly photoresist peeling method in which the reuse rate of the aqueous peeling solution is increased.
BACKGROUND ART [0002] Photo-lithography processes are widely used to form a certain pattern on a substrate in a process of manufacturing a microcircuit of a semiconductor integrated circuit or a liquid crystal display device.
In such a photolithography process, a photoresist is uniformly applied to metal and metal oxide electrode layers formed on a substrate, and selectively exposed and developed to form a photoresist pattern. Then, the photoresist pattern is formed using the patterned photoresist film as a mask, And the metal oxide electrode layer. Thereafter, the process proceeds to the step of removing the unnecessary photoresist layer with the peeling liquid.
It is advantageous for the exfoliation liquid used herein to have an excellent peeling ability which can peel off the photoresist in a short time and does not leave a photoresist residue on the substrate. For this purpose, the conventional peeling liquid contains a large number of environmentally harmful organic substances. Recently, the amount of the peeling liquid has been rapidly increased, resulting in problems due to strong toxicity and environmental pollution due to the peeling liquid. Environmental regulations on the use of liquids have also been strengthened.
In order to solve such problems, the ratio of the exfoliant, the application of additives, and the development of refining technology are increasing. Water-based exfoliative compositions in which various organic solvents are mixed with water-soluble alkanolamine as an essential component have also been proposed.
However, even in the case of such a water-based peeling composition, there still exists a problem of treating the peeling waste solution which is generated after being used in the process. Particularly, since the photolithography process and the photoresist stripping process are repeatedly performed in many steps in the manufacturing process, a large amount of photoresist stripping liquid is generated, and the amount of the stripping solution is increased by rapid enlargement of the display substrate area such as a liquid crystal display device The demand for the treatment of the stripping waste liquid is further increased.
Conventionally, there is a method of incineration treatment by such a method of treating the exfoliated waste liquid. However, there is an uneconomical aspect in which the incineration gas is released to the atmosphere, which may adversely affect the environment and the recyclable components of the exfoliated waste liquid are also discarded do.
Another method for treating the stripping waste liquid is to recover the stripping waste liquid to remove the impurities in the stripping waste liquid below the reference value, and to replenish the lost components during the process, thereby regenerating the stripping liquid.
For example, Korean Patent No. 10-1330654 discloses a method for further regenerating a high-boiling stripping solvent that has been discarded as a distillation residue with high boiling point impurities through primary, secondary, tertiary and quaternary distillation apparatus Korean Patent No. 10-0390567 discloses a method of automatically analyzing the components of a pulmonary detachment liquid in real time using a near infrared ray spectroscope or the like to determine the life span in comparison with a reference value and replenishing necessary components to reuse .
However, the impurities contained in the stripping waste liquid are various, and the characteristics are different for each component, which is not easy to remove, and these conventional regeneration methods are unsatisfactory in terms of purity and regeneration yield. In addition, in such a regeneration process, complex processes for purifying harmful substances must be repeatedly operated many times, and a tremendous processing cost is required accordingly.
Therefore, there is still a need to develop a photoresist stripping method that reduces the rate of occurrence of waste liquid generated in the process or raises the reusability of the stripping liquid, thereby reducing the process cost and solving environmental problems.
SUMMARY OF THE INVENTION It is an object of the present invention to provide an eco-friendly photoresist stripping method which reduces the cost of the process by increasing the reuse rate of the photoresist stripping solution to solve the above problems.
In order to achieve the above object,
i) forming a photoresist layer on a substrate on which a metal and metal oxide electrode layer is deposited,
ii) exposing the photoresist layer to form a photoresist pattern,
iii) etching the substrate with the photoresist pattern,
iv) immersing the substrate in a water-based exfoliation liquid, and
v) extracting the substrate from the aqueous stripping solution and stripping the photoresist layer from the substrate
The present invention also provides a method for peeling a photoresist.
In one embodiment according to the first aspect of the invention, the exfoliation of the photoresist may occur only in step v).
In another embodiment according to the first aspect of the invention, step iv) may be maintained for 15 to 20 seconds.
In another embodiment according to the first aspect of the present invention, in step v) the substrate may be extracted from the aqueous stripping liquid at an extraction angle of 60 to 90 degrees.
In another embodiment according to the first aspect of the present invention, the aqueous detachment liquid comprises 20 to 30% by weight of a detachment stock solution comprising ethanolamine and a water-soluble organic solvent, based on the total weight of the aqueous detachment solution; And 70 to 80% by weight of water.
In another embodiment according to the first aspect of the present invention, in step iv) the temperature of the aqueous stripping solution may be between 30 캜 and 50 캜.
In another embodiment according to the first aspect of the present invention, the photoresist layer formed on the substrate in step i) may be a dry film resist layer.
In another embodiment according to the first aspect of the present invention,
i) forming a photoresist layer on a substrate on which a metal and metal oxide electrode layer is deposited,
ii) exposing the photoresist layer to form a photoresist pattern,
iii) etching the substrate with the photoresist pattern,
iv) immersing the substrate in a water-based exfoliation liquid, and
v) extracting the substrate from the aqueous stripping solution and stripping the photoresist layer from the substrate
The photoresist stripping method comprising:
vi) cleaning the substrate
. ≪ / RTI >
According to the present invention, in removing a photoresist layer generally used in a semiconductor or a display manufacturing process, it is possible to provide a method of peeling an eco-friendly photoresist by reducing the generation rate of harmful substances by using an aqueous peeling solution .
In addition, the method of removing the photoresist according to the present invention minimizes the contaminants remaining in the exfoliation liquid during the exfoliation process of the photoresist layer, so that the exfoliation liquid can be reused without a separate recovery and recovery process of the exfoliation waste.
In addition, the generation rate of the stripping liquid can be lowered and the amount of the stripping liquid used can be minimized in the stripping process of the photoresist.
Therefore, it is possible to peel the photoresist layer in an environmentally friendly and economical manner while simplifying the display manufacturing process.
Figure 1 is a schematic representation of a typical photolithographic process.
2 is a graph showing UV transmittance measured based on a wavelength of 550 nm of the ITO electrode manufactured in the embodiments of the present invention.
3 is a graph showing resistance values of the ITO electrode manufactured in the embodiments of the present invention.
Hereinafter, the method for peeling the photoresist according to the specific embodiments of the present invention will be described in more detail.
In one embodiment of the present invention,
i) forming a photoresist layer on a substrate on which a metal and metal oxide electrode layer is deposited,
ii) exposing the photoresist layer to form a photoresist pattern,
iii) etching the substrate with the photoresist pattern,
iv) immersing the substrate in a water-based exfoliation liquid, and
v) extracting the substrate from the aqueous stripping solution and stripping the photoresist layer from the substrate
.
The photoresist stripping method according to the present invention can be applied to general semiconductor and display manufacturing processes.
For example, as shown in FIG. 1, a metal or metal oxide electrode layer 2 is deposited on the substrate 1 in the formation of fine electrodes and circuits, and then the photoresist layer 3 is coated. Then, ultraviolet rays (UV) are applied to the exposure mask 4 to form a photoresist pattern. Thereafter, the uncured portions of the photoresist are developed, and finally the unnecessary portions of the photoresist are removed by using the peeling solution to complete the circuit. At this time, the substrate having the photoresist layer is subjected to a dipping method in which the substrate is immersed in the prepared water-based exfoliation liquid, and then the substrate is again extracted, whereby the exfoliation process can be proceeded with the exfoliation liquid remaining on the substrate.
The metal and the metal oxide deposited on the substrate are not particularly limited as long as they can be used as an electrode layer. Such metals and metal oxides include, but are not limited to, aluminum (Al), copper (Cu), indium-tin oxide (ITO), and the like.
In the photoresist stripping method according to the present invention, there is no particular limitation on the method of depositing, exposing, developing, etching, and etching the photoresist layer, and may be performed according to a process commonly known in the art.
In the present invention, a method of peeling a photoresist uses a dipping method in which a substrate to be peeled is dipped in a large amount of peeling liquid.
According to one embodiment of the present invention, in step iv), the substrate may be immersed in the aqueous stripping solution for a certain period of time, and a typical technician can appropriately select the dipping time as required. For example, the dipping time may be a time until the photoresist layer is fully activated in the substrate, and the photoresist residue may not be generated in the water-based stripping solution, and may be added as a stripping solution adhered to the substrate It can be appropriately selected as the time when residue can not be left by proceeding peeling.
In a preferred embodiment of the present invention, this dipping time is not limited to 15 seconds to 20 seconds, more preferably 16 to 18 seconds.
According to a preferred embodiment of the invention, the exfoliation of the photoresist can be carried out only after the substrate has been extracted from the aqueous stripper, i. E. In step v). In this case, the substrate in the aqueous detachment solution is extracted before the separation of the photoresist is started, and the separation can proceed due to the residual amount of the detachment solution adhered to the substrate at the time of extraction. For example, after the appropriate dipping time, the substrate can be extracted from the aqueous stripping solution, and the extracted substrate can be left at room temperature and in the atmosphere to perform the photoresist stripping.
When the substrate is extracted from the aqueous detachment solution, the viscosity, extraction speed or extraction angle of the aqueous detachment solution can be controlled to be constant. For example, when the substrate is extracted, the extraction angle formed between the substrate and the water interface may be 30 to 90 degrees, and the higher the angle, the more preferable.
In one embodiment of the present invention, the extraction angle is more preferably 60 to 90 degrees.
This extraction angle can be an important factor in maximizing the quantitative portion of the water-based exfoliation liquid flowed out from the surface of the substrate hydrodynamically in the process of being subjected to the extraction process after the dipping. Therefore, the difference in the amount of the exfoliating liquid on the substrate surface depending on the extraction angle at the time of extracting the substrate from the exfoliation liquid may occur, which may ultimately affect the performance of delaminating the unnecessary photoresist layer.
After the substrate is extracted from the aqueous stripping solution, the substrate is left standing, and the photoresist is peeled off with the stripping solution deposited on the substrate. The peeling time means a time taken for the peeling to be completed after the peeling of the film starts from the initial surface. Such peeling time may be different depending on the kind of the photoresist, the composition ratio of the water-based peeling solution, and the like.
In one embodiment of the present invention, the peeling time is 30 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 1 minute or less.
The peeling liquid used in the peeling method of the photoresist according to the present invention is an aqueous peeling liquid, which can overcome the problems of the organic peeling liquid relating to environmental problems due to high manufacturing cost and toxic substances and process stability. There is no particular limitation on such a water-based stripping solution, and a person skilled in the art can select a suitable water-based stripping solution well known in the art according to the desired properties.
The water-based exfoliation liquid may include an organic amine compound, which is an alkaline compound, and a polar solvent. The organic amine compounds include, for example, aliphatic amines, aromatic amines, cyclic amines, and the like.
In one embodiment of the invention, the organic amine compound is an alkanolamine compound.
The alkanolamine compound is strongly alkaline and penetrates into the matrix of the photoresist in the process to break or weaken the intramolecular or intermolecular bonds, thereby facilitating the peeling of the photoresist. Examples of such alkanolamine compounds include monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethylaminoethanol, Aminoethanol, ethylaminoethanol, 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine, monoisopropanolamine and dibutanolamine. May be mixed and used. The alkanolamine compound is preferably ethanolamine.
The aqueous stripping liquid containing the organic amine compound can provide the same level of processing time and peel capability as the organic stripping liquid.
The polar solvent has excellent compatibility with water and an organic compound and can act as a solvent for dissolving the photoresist. Such polar solvents include N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide ), N-methylformamide (NMF), tetramethylene sulfone, butyl diglycol (BDG), ethyl diglycol (EDG), methyl diglycol (MDG), triethylene glycol glycol, TEG, diethyleneglycolmonoethylether (DEM), diethyleneglycolmonoethylether, or a mixture thereof. However, the present invention is not limited thereto.
The polar solvent can effectively remove the peeling liquid in the cleaning process of the substrate using deionized water or the like after peeling off the photoresist.
Such alkanolamine compounds and polar solvents may be contained in the aqueous stripping liquid in an appropriate ratio.
The aqueous detachment solution may further contain other additives such as an alkanolamine compound and a polar solvent such as a surfactant, a corrosion inhibitor, a preservative, and the like, and there is no particular limitation thereon.
The water-based exfoliating liquid used in the exfoliation method of the photoresist according to the present invention can be prepared by mixing the exfoliating stock solution with water. At this time, the undiluted undiluted solution and water can be mixed in various ratios. In order to have an adequate peelability, for example, based on the total weight of the aqueous detachment solution, 5 to 30 wt% of the undiluted undiluted solution, preferably 20 To 30% by weight. If the water-based stripping solution contains less than 5% by weight of the stripping solution, it may not have sufficient stripping performance. If the aqueous stripping solution contains more than 30% by weight of the stripping solution, cleaning after the stripping of the photoresist may not be performed properly have.
Within the weight range of the aqueous detachment solution, the higher the ratio of the undiluted solution to the undiluted solution is, the better the peeling effect is, and the amount of the detachment solution can be reduced during the peeling step.
On the other hand, based on the total weight of the aqueous detachment solution, the aqueous detachment solution may contain 70 to 95% by weight, preferably 70 to 80% by weight of water.
In one embodiment of the present invention, the temperature of the aqueous stripping solution in which the substrate is immersed in step iv) may be from room temperature to 50 캜, and preferably from 30 캜 to 50 캜.
The type of photoresist to which the photoresist stripping method according to the present invention can be applied is not particularly limited and may be selected from suitable photoresists known in the art. There is no particular limitation on the type of DFR (dry film resist).
Types of photoresist include positive photoresist and negative photoresist.
Generally, the constituent components of the positive photoresist include a solvent, a novolak resin, a PAC (Photo Active Compound), and the like. Therefore, if it is not sensitized, it will not dissolve in the developer in the state of azo coupling between PAC and novolak resin. However, when UV light is received, some functional group of PAC is changed into - COOH, Dissolved in an alkali developing solution. Therefore, since the exposed part is removed, the same pattern as the mask pattern is left, so it is called a positive type.
On the other hand, in the case of a general negative photoresist, a chemical amplification type is often used. The constituent components include a solvent, a resin, a cross-linker, and a photo acid generator (PAG). In this case, if the UV light is not received, the resin has a functional group such as -OH to easily dissolve in the alkali developing solution. However, when UV light is received, the PAG is decomposed to generate acid, and a post exposure bake (PEB ), And the crosslinking agent reacts with the -OH functional group of Resin to catalyze the resins to connect with each other. Therefore, since the number of functional groups capable of easily dissolving in the developer is decreased, the exposed portion remains, which is not dissolved in the developing solution. Therefore, the negative pattern is called a negative type because the pattern of the reversed phase remains.
The photoresist to which the present invention is effectively applied is preferably a negative type photoresist, more preferably dry film resist (DFR).
In the present invention, there is no particular restriction on the specific constituents of such photoresist, but the resist to which it is effectively applied is a photoresist film composed of a novolak-based phenol resin and a photoactive compound based on diazonaphthoquinone, It is also effective for a photoresist film.
In one embodiment of the present invention, the method further includes a step of cleaning the substrate to remove the peeling liquid and the peeled photoresist layer remaining on the substrate after the substrate is extracted from the aqueous peeling liquid and the photoresist layer is peeled off . The cleaning process can be performed using an organic solvent or water. As the organic solvent, a lower alcohol is preferable, and for example, isopropyl alcohol can be used. The specific cleaning method is not particularly limited, and any suitable method known in the art can be used.
Further, after the cleaning treatment, an additional step such as a drying step can be carried out if necessary.
In the method of peeling the photoresist according to the present invention, since the substrate is immersed in the aqueous peeling solution and then extracted to remove the photoresist, the content of the photoresist residue and the impurities peeled off in the peeling solution in the aqueous system can be minimized. Therefore, according to the peeling method of the photoresist according to the present invention, since the water-based peeling solution may not require any additional recovery, filtration and regeneration steps, the process can be simplified, and the water-based peeling solution can be immediately reused, Improvement and cost reduction can be achieved.
In addition, since the steps (i) to (v) are repeatedly carried out without replacing the water-based exfoliation solution, the amount of the water-based exfoliation solution can be minimized, and the rate of generation of the exfoliation solution can be reduced. Therefore, unlike the existing exfoliation process, Can be expected.
Hereinafter, the method for peeling the photoresist according to the present invention will be described in more detail in Examples, but the present invention is not limited to the scope of the following embodiments.
[Example]
Example 1
An ITO thin film was deposited on a non-alkaline glass substrate having a size of 370 x 470 mm, and then patterned with a blue DFR (dry film photoresist) film having a thickness of 40 μm to form an electrode of the light emitting device.
PR4031 purchased from EOTECH Co., Ltd. was used as an aqueous detachment stock solution and mixed with distilled water to prepare a water detachment solution. At this time, based on the weight of the final aqueous detachment solution, 20% by weight of the aqueous detachment stock solution and 80% by weight of distilled water were mixed. The aqueous stripping solution was transferred to an 80 ml beaker at which the temperature of the stripping solution was 40 占 폚.
The glass substrate patterned with the DFR prepared above was immersed therein. The glass substrate immersed after 17 seconds was slowly extracted from the beaker while keeping the extraction angle at 30 degrees. At this time, there was no peeled DFR sludge in the water-based peeling solution in the beaker. The glass substrate extracted out of the beaker was allowed to stand in the air for 4 minutes and the peeling was proceeded with the residual adhesive detachment solution on the surface.
Then, the glass substrate was washed with deionized water. To measure the degree of peeling of the peeled glass substrate, the UV-visible transmittance was measured based on a wavelength of 550 nm and the sheet resistance was measured using a Hall effect measuring apparatus , And the measurement results are shown in Table 2 below.
Example 2
Except that the immersed glass substrate was slowly extracted from the beaker while maintaining the extraction angle at 60 degrees.
Example 3
The procedure of Example 1 was repeated except that the immersed glass substrate was slowly extracted from the beaker while maintaining the extraction angle at 90 degrees.
Example 4
Example 1 was repeated except that PR4031 purchased from EOTECH was used as an aqueous detachment stock solution and the aqueous detachment solution was mixed with 25 wt% of distilled water and 75 wt% of distilled water based on the weight of the final aqueous detachment solution. .
Example 5
The procedure of Example 4 was repeated except that the immersed glass substrate was slowly extracted from the beaker while maintaining the extraction angle at 60 degrees.
Example 6
The same procedure as in Example 4 was carried out except that the immersed glass substrate was slowly extracted from the beaker while keeping the extraction angle at 90 degrees.
Example 7
Except that PR4031 purchased from EOTECH was used as a stock solution for aqueous detachment, and the amount of the aqueous detachment stock solution was 30 wt% and distilled water was 70 wt% based on the weight of the final aqueous detachment solution. .
Example 8
The procedure of Example 7 was repeated except that the immersed glass substrate was slowly extracted from the beaker while maintaining the extraction angle at 60 degrees.
Example 9
The procedure of Example 7 was repeated except that the immersed glass substrate was slowly extracted from the beaker while maintaining the extraction angle at 90 degrees.
Weight ratio
Exposure time (seconds)
(transmittance,% T)
(ohm / sq)
According to Table 2, in order to precisely verify the degree of peeling of the ITO thin films prepared in Examples 1 to 9, the measured UV transmittance showed a transmittance of 85% or more based on a wavelength of 550 nm as a reference. In other words, it can be seen that the excellent peeling degree in all of the use conditions of Examples 1 to 9 is exhibited. Specifically, it can be seen that the higher the composition ratio of the peeling stock solution is, and the better the peeling state is, . In addition, the sheet resistance measurements of the ITO thin films prepared in Examples 1 to 9 were all within 10 ohm / sq.
Therefore, the method of peeling the photoresist according to the present invention is characterized in that the substrate is immersed in a water-based peeling solution, and the peeling is carried out with only a small amount of peeling solution adhered to the substrate before the peeling is activated, It can be confirmed that the usage rate can be increased.
The embodiments described herein are intended to be illustrative only and not for limiting the scope of the present invention. Accordingly, the scope of the present invention should be construed as being included in the scope of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
1: substrate
2: electrode layer
3: Photoresist layer
4: Exposure mask
Claims (8)
ii) exposing the photoresist layer to form a photoresist pattern,
iii) etching the substrate with the photoresist pattern,
iv) immersing the substrate in an aqueous stripping solution having a temperature of 30 ° C to 50 ° C for 15 seconds to 20 seconds, and
v) extracting the substrate from the aqueous detachment solution after the immersion for 15 to 20 seconds at an extraction angle of 60 to 90 degrees, and
vi) peeling the photoresist layer from the substrate with the substrate exposed to the atmosphere,
Based on the total weight of the water-based exfoliation liquid, 20 to 30% by weight of the exfoliating stock solution containing ethanolamine and a water-soluble organic solvent; And 70 to 80% by weight of water,
The water-based stripping solution contains an organic amine compound and a polar solvent,
As the polar solvent, there may be used N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylformamide (DMF) (NMG), tetramethylene sulfone, butyl diglycol (BDG), ethyl diglycol (EDG), methyl diglycol (MDG), triethylene glycol (TEG) A method of peeling a photoresist comprising glycol monoethyl ether (DEM), diethyleneglycolmonoethylether, or a mixture thereof.
vii) cleaning the substrate after the removal of the photoresist layer.
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