CN116149148A - Stripper composition for removing photoresist and stripping method of photoresist using the same - Google Patents
Stripper composition for removing photoresist and stripping method of photoresist using the same Download PDFInfo
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- CN116149148A CN116149148A CN202211149997.8A CN202211149997A CN116149148A CN 116149148 A CN116149148 A CN 116149148A CN 202211149997 A CN202211149997 A CN 202211149997A CN 116149148 A CN116149148 A CN 116149148A
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- 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
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Abstract
The present disclosure relates to a stripper composition for removing photoresist having improved photoresist solubility and inhibiting corrosion of an underlying metal film during a stripping process while having excellent stripping force to the photoresist, and a stripping method of photoresist using the same.
Description
Technical Field
The present disclosure relates to a stripper composition for removing photoresist and a stripping method of photoresist using the same, and more particularly, to a stripper composition for removing photoresist which suppresses corrosion of a lower metal film during stripping while having excellent stripping ability of photoresist and has improved photoresist solubility, and a stripping method of photoresist using the same.
Background
The manufacturing process of the microcircuit or semiconductor integrated circuit of the liquid crystal display device includes the steps of: forming various lower films, for example, a conductive metal film made of aluminum, aluminum alloy, copper alloy, molybdenum, or molybdenum alloy, or an insulating film such as a silicon oxide film, a silicon nitride film, or an acrylic (acryl) insulating film, on a substrate; uniformly coating a photoresist on such a lower film; optionally exposing and developing the coated photoresist to form a photoresist pattern; and patterning the lower film using the photoresist pattern as a mask. After these patterning steps, a process of removing the photoresist remaining on the lower film is performed. For this purpose, a stripping composition for removing the photoresist is used.
Previously, stripper compositions comprising an amine compound, a polar protic solvent, a polar aprotic solvent, and the like have been known and mainly used. These stripper compositions are known to exhibit a degree of photoresist removal and stripping capability.
However, in the case of stripping a large amount of photoresist, these conventional stripper compositions promote decomposition of amine compounds with the lapse of time, and thus have a problem in that stripping and rinsing capacities are lowered with the lapse of time. In particular, depending on the time of application of the stripper composition, these problems may be further exacerbated when a portion of the remaining photoresist is dissolved in the stripper composition.
Further, when the photoresist modified by dry etching remains on the substrate, there is a problem of a film separation phenomenon or a wiring disconnection phenomenon occurring during the course of post-processing, which affects TFT yield.
Therefore, there is a need to develop a new stripper composition that has excellent stripping ability even under hard baking conditions, suppresses corrosion of the underlying metal film, and has improved photoresist solubility.
Disclosure of Invention
Technical problem
An object of the present application is to provide a stripper composition for removing photoresist, which suppresses corrosion of a lower metal film during stripping while having excellent stripping ability for photoresist, and has improved photoresist solubility, and a stripping method of photoresist using the same.
It is another object of the present application to provide a photoresist stripping method using the stripper composition for removing photoresist.
Technical proposal
Provided herein is a stripper composition for removing photoresist, comprising: primary or secondary chain amine compounds; a cyclic amine compound; amide compounds in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and having a boiling point of 180 ℃ or higher; a protic solvent; and a corrosion inhibitor, wherein the amide compound having a boiling point of 180 ℃ or higher, in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms, is contained in an amount of 60 to 90 wt%, and wherein the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is 100:1 to 1:1, relative to the total weight of the stripper composition.
Also provided herein are methods for stripping photoresist comprising the step of stripping photoresist using a stripper composition for removing photoresist.
A stripper composition for removing photoresist and a method of stripping photoresist using the same according to specific embodiments of the present disclosure will be described in more detail below.
The technical terms used herein are for the purpose of describing exemplary embodiments only and are not intended to limit the scope of the present invention. The singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be understood that the terms "comprises," "comprising," "includes," "including," "having," and the like are used herein to specify the presence of stated features, integers, steps, components, or groups thereof, but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
While the present disclosure is susceptible to various forms and modifications, specific embodiments will be shown and described in detail. It is not intended to limit the disclosure to the form disclosed, however, and it is to be understood that all modifications, equivalents, or alternatives falling within the spirit and scope of the disclosure are included in the disclosure.
According to one embodiment of the present disclosure, there may be provided a stripper composition for removing photoresist, comprising: primary or secondary chain amine compounds; a cyclic amine compound; amide compounds in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and having a boiling point of 180 ℃ or higher; a protic solvent; and a corrosion inhibitor, wherein the amide compound having a boiling point of 180 ℃ or higher, in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms, is contained in an amount of 60 to 90 wt%, and wherein the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is 100:1 to 1:1, relative to the total weight of the stripper composition.
The present inventors have conducted intensive studies on a stripper composition for removing a photoresist, and found through experiments that: the stripper composition for removing photoresist, which contains all of the above components, suppresses corrosion of the underlying metal film during stripping while having excellent stripping ability for photoresist, and has improved photoresist solubility, thereby completing the present disclosure.
As described above, the stripper composition for removing photoresist of this embodiment contains an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and has a boiling point (bp) of 180 ℃ or more, and an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and has a boiling point (bp) of 180 ℃ or more is contained in an amount of 60 to 90 wt%, and a weight ratio of a primary or secondary chain amine compound to a cyclic amine compound is 100:1 to 1:1, with respect to the total weight of the stripper composition, so that stripping ability can be improved and photoresist solubility can be improved, as compared with conventional cases.
Amide compounds in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and having a boiling point (bp) of 180 ℃ or higher can advantageously dissolve the amine compound with aprotic polar organic solvents, allow the stripper composition for removing photoresist to effectively permeate onto the lower film, and can function to improve stripping ability, rinsing ability, etc. of the stripper composition.
Furthermore, the amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms has a boiling point (bp) of 180 ℃ or more, or 182 ℃ or more, or 185 ℃ or more, or 190 ℃ or more, or 250 ℃ or less, or 210 ℃ or less, or 180 ℃ to 250 ℃, or 180 ℃ to 210 ℃, or 182 ℃ to 250 ℃, or 182 ℃ to 210 ℃, or 185 ℃ to 250 ℃, or 185 ℃ to 210 ℃, or 190 to 250 ℃, or 190 to 210 ℃. When a photoresist is peeled using a stripper composition containing an amide compound having a predetermined boiling point, loss due to volatilization of the amide compound can be reduced and decomposition of the amine compound over time is hardly caused, so that the stripper composition of one embodiment can maintain physical properties such as excellent stripping and rinsing ability for a long period of time.
The boiling point may be applied without limitation to a generally known organic solvent measurement method (e.g., a simple distillation apparatus, etc.), and may be measured at normal temperature (temperature of 20 ℃ to 30 ℃) and atmospheric pressure (pressure of 1 atmosphere).
Meanwhile, when the boiling point (bp) of the amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms is too high, the recovery efficiency may be lowered in the subsequent distillation of the waste liquid under reduced pressure, and thus, the boiling point is preferably 250 ℃ or less.
Meanwhile, more specifically, an amide compound having a boiling point (bp) of 180 ℃ or more and nitrogen substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms may be contained in an amount of 60 wt% or more, 65 wt% or more, or 70 wt% or more, and 90 wt% or less, 85 wt% or less, or 80 wt% or less, with respect to the total weight of the stripper composition, based on the total weight of the stripper composition.
When the stripper composition for removing photoresist of one embodiment contains an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and the boiling point (bp) is 180 ℃ or more in the above content, the solubility of the photoresist is increased, excellent stripping ability and the like can be ensured, and stripping and rinsing ability can be maintained for a long period of time.
In addition, when the photoresist used remains on the substrate, a film separation phenomenon or a wire disconnection phenomenon occurs during the course of the post-process, which affects the process yield. Since the stripper composition for removing photoresist of one embodiment contains an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and a boiling point (bp) of 180 ℃ or more in the above content, the solubility of the photoresist is increased, the possibility of photoresist residues remaining on the substrate after the stripping process is reduced, and thus process economy and efficiency can be improved.
Meanwhile, when the content of the amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and the boiling point (bp) is 180 ℃ or more is less than 60 wt%, based on the total weight of the stripper composition, there may be problems in that the stripping ability is lowered and the photoresist remains on the substrate. When the content of the amide compound exceeds 90% by weight, there may be a problem in that the stripping liquid remains on the surface without being washed in the washing step.
Specifically, an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and the boiling point (bp) is 180 ℃ or higher may have the structure of the following chemical formula 1.
[ chemical formula 1]
Wherein, in the chemical formula 1,
R 1 is hydrogen, methyl, ethyl or propyl,
R 2 is a methyl group or an ethyl group,
R 3 is hydrogen or a linear or branched alkyl radical having 1 to 5 carbon atoms, and
R 1 and R is 3 May be combined with each other to form a ring.
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms are not limited, but for example, methyl, ethyl, propyl, butyl, isobutyl, pentyl and the like can be used.
An amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and has a boiling point (bp) of 180 ℃ or higher may be at least one selected from the group consisting of: n-methylformamide (NMF), N-ethylformamide (NEF), N-methyl-2-pyrrolidone (NMP) and N-ethyl-2-pyrrolidone (NEP).
Meanwhile, the stripper composition for removing photoresist may include a primary or secondary chain amine compound and a cyclic amine compound.
The amine compound including a primary or secondary chain amine compound and a cyclic amine compound may provide the stripper composition for removing photoresist with stripping ability of photoresist and may function to dissolve and remove photoresist. In particular, the primary or secondary chain amine compound may function to improve the stripping ability, and the cyclic amine compound may function to improve the stripping ability and minimize damage to the metal wiring.
In particular, since the stripper composition for removing a photoresist of this embodiment contains one kind of primary or secondary chain amine compound and one kind of cyclic amine compound, the removal rate of Cu oxide is improved, the photoresist does not remain on the insulating film after stripping the insulating film as in the conventional case, metal oxide which may be generated on the lower metal film (e.g., lower Cu wiring) is easily removed, and when a transparent conductive film such as ITO is formed, a film separation phenomenon between the insulating film and the lower metal film can be prevented.
Meanwhile, the weight ratio between the primary or secondary chain amine compound and the cyclic amine compound may be 100:1 to 1:1, or 80:1 to 1:1, or 50:1 to 1:1, or 10:1 to 1:1, or 100:1 to 1.5:1, or 80:1 to 1.5:1, or 50:1 to 1.5:1, or 10:1 to 1.5:1. Specifically, in the formula, it means a weight ratio of a primary or secondary chain amine compound to a cyclic amine compound. For example, the weight ratio of the primary or secondary chain amine compound may be 1 to 100 parts by weight, or 1 to 80 parts by weight, or 1 to 50 parts by weight, or 1 to 10 parts by weight, or 1.5 to 100 parts by weight, or 1.5 to 80 parts by weight, or 1.5 to 50 parts by weight, or 1.5 to 10 parts by weight, relative to 1 part by weight of the cyclic amine compound.
At this time, when the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound exceeds 100:1, corrosion occurs on Cu metal or TFT, and problems such as film separation may occur due to adhesion problems with the next insulating film or metal. When the weight ratio is less than 1:1, the decomposing ability of the photoresist is reduced and remains on the substrate, which may cause problems of foreign matters such as film separation.
That is, the stripper composition for removing photoresist of this embodiment contains a primary or secondary chain amine compound and a cyclic amine compound, and the content of the cyclic amine compound is equal to or relatively smaller than that of the primary or secondary chain amine compound, thereby being capable of improving stripping ability and removal ability of metal oxide in the metal-containing lower film.
Meanwhile, the total content of the primary or secondary chain amine compound and the cyclic amine compound may be 1 wt% or more, 3 wt% or more, or 5 wt% or more, 20 wt% or less, 15 wt% or less, or 10 wt% or less, with respect to the total weight of the stripper composition, more specifically, based on 100 wt% of the total weight of the stripper composition.
According to the content range of such an amine compound, the stripper composition of one embodiment can not only exhibit excellent stripping ability and the like, but also can reduce the decrease in process economy and efficiency caused by an excessive amount of amine, and reduce the generation of waste liquid and the like.
If the amine compound is contained in an excessively large amount, it may cause corrosion of the lower film (e.g., copper-containing lower film), and a large amount of corrosion inhibitor may be required to suppress this. In this case, a large amount of corrosion inhibitor may be adsorbed and remain on the surface of the lower film due to the large amount of corrosion inhibitor, thereby deteriorating the electrical characteristics of the copper-containing lower film.
In particular, if the total content of the primary or secondary chain amine compound and the cyclic amine compound is less than 1 wt% with respect to the total weight of the stripper composition, the stripping ability of the stripper composition for removing photoresist may be reduced, and when the total content exceeds 20 wt% with respect to the total weight of the composition, inclusion of an excessive amount of the amine compound may result in a reduction in process economy and efficiency.
Further, within the content range of the amine compound, it can be used by adjusting the weight ratio between the above-mentioned primary or secondary chain amine compound and the cyclic amine compound.
The primary or secondary chain amine compound may include at least one compound selected from the group consisting of: 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, monoethanolamine, aminoethylethanolamine, N-methylethanolamine, and diethanolamine, but are not limited thereto.
The cyclic amine compound may comprise an intramolecular tertiary amine structure. Tertiary amine means a structure in which three organic functional groups (other than hydrogen) are bonded to one nitrogen atom, and the cyclic amine compound may contain at least one nitrogen atom of the tertiary amine. As a specific example, in the case of 1-imidazolidine ethanol, the nitrogen atom in the ring bonded to ethanol corresponds to the nitrogen atom of a tertiary amine.
Further, the cyclic amine compound may be a saturated amine compound. Saturated amine compounds mean compounds in which the molecule consists of only single bonds and does not contain unsaturated bonds (double or triple bonds).
The cyclic amine compound may include at least one compound selected from the group consisting of: 1-imidazolidineethanol, 1- (2-hydroxyethyl) piperazine and N- (2-aminoethyl) piperazine.
Meanwhile, the stripper composition for removing the photoresist may include a protic solvent. The protic solvent is a polar organic solvent, allows the stripper composition for removing photoresist to better permeate onto the lower film, thereby contributing to excellent stripping ability of the stripper composition for removing photoresist, and can effectively remove stains on the lower film (e.g., copper-containing film), thereby improving rinsing ability of the stripper composition for removing photoresist.
The protic solvent may comprise a compound based on an alkylene glycol monoalkyl ether. More specifically, the alkylene glycol monoalkyl ether compound may include diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, or a mixture of two or more thereof.
Further, in view of the excellent wettability of the stripper composition for removing a photoresist and the improved stripping ability and rinsing ability resulting therefrom, diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl Ether (EDG), diethylene glycol monobutyl ether (BDG), diethylene glycol mono-tert-butyl ether (DGtB), or the like may be used as the alkylene glycol monoalkyl ether compound.
The protic solvent may be contained in a remaining content excluding a primary or secondary chain amine compound, a cyclic amine compound, an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and having a boiling point (bp) of 180 ℃ or higher, a corrosion inhibitor, and the like, with respect to the total weight of the composition.
For example, the protic solvent may be included in an amount of 1 to 50 wt.%, or 5 to 45 wt.%, or 10 to 40 wt.%, relative to the total weight of the composition, more specifically, based on 100 wt.% of the total weight of the stripper composition. By satisfying this content range, excellent stripping ability and the like of the stripper composition for removing the photoresist can be ensured, and the stripping ability and rinsing ability can be maintained for a long period of time.
In another aspect, a stripper composition for photoresist removal may include a corrosion inhibitor.
The above corrosion inhibitor can inhibit corrosion of a metal-containing lower film such as a copper-containing film when the photoresist pattern is removed using a stripper composition for removing the photoresist.
As the corrosion inhibitor, at least one selected from triazole-based compounds and imidazole-based compounds may be used.
At this time, examples of the triazole-based compound are not particularly limited, but for example, they may be at least one selected from the following: 2,2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol and 4,5,6, 7-tetrahydro-1H-benzotriazol.
Further, examples of the imidazole-based compound are not particularly limited, but may be, for example, 2-mercapto-1-methylimidazole.
On the other hand, the corrosion inhibitor may be included in an amount of 0.01 to 10 wt%, or 0.01 to 5.0 wt%, or 0.01 to 1.0 wt%, relative to the total weight of the stripper composition, more specifically, based on 100 wt% of the total weight of the composition. When the content of the corrosion inhibitor is less than 0.01 wt% relative to the total weight of the composition, it may be difficult to effectively inhibit corrosion of the lower film. In addition, when the content of the corrosion inhibitor exceeds 10 wt% relative to the total weight of the composition, a large amount of the corrosion inhibitor may be adsorbed and remain on the lower film, thereby reducing the electrical characteristics of the copper-containing lower film, particularly the copper/molybdenum metal film.
Furthermore, the stripper composition for removing photoresist may contain a silicone-based nonionic surfactant in an amount of less than 0.001 wt% or less than 0.0001 wt% relative to the total weight of the stripper composition, more specifically, based on 100 wt% of the total weight of the composition. More preferably, the stripper composition for removing photoresist contains substantially no silicone-based nonionic surfactant, or may contain only trace amounts to the extent of containing little silicone-based nonionic surfactant.
When the content of the silicone-based nonionic surfactant is increased to more than 0.001 wt% or more than 0.001 wt% with respect to the total weight of the composition, a problem of variation in metal contact resistance may occur.
In particular, the silicone-based nonionic surfactant may include a polysiloxane-based polymer. More specifically, examples of the polysiloxane-based polymer are not particularly limited, but, for example, polyether-modified acrylic-functional polydimethylsiloxane, polyether-modified siloxane, polyether-modified polydimethylsiloxane, polyethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified hydroxy-functional polydimethylsiloxane, polyether-modified dimethylpolysiloxane, modified acrylic-functional polydimethylsiloxane, or a mixture of two or more thereof, and the like may be used.
The stripper composition for removing the photoresist may further contain conventional additives as needed, and the specific type or content of the additives is not particularly limited.
In addition, the stripper composition for removing photoresist may be prepared according to a general method of mixing the above components. There is no particular limitation in the specific method of preparing the stripper composition for removing photoresist.
In another aspect, according to another embodiment of the present invention, there may be provided a method for stripping photoresist, the method including the step of stripping photoresist using the stripper composition for removing photoresist according to one of the above embodiments.
The method for stripping photoresist of one embodiment may include the steps of: forming a photoresist pattern on a substrate having a lower film formed therein; patterning the lower film with a photoresist pattern; and stripping the photoresist using the stripper composition for removing the photoresist according to one of the above embodiments.
The description about the stripper composition for removing photoresist includes a detailed description about one of the above embodiments.
In particular, a method of stripping photoresist may include: a step of forming a photoresist pattern on a substrate on which a lower film to be patterned is formed by a photolithography process, a step of patterning the lower film using the photoresist pattern as a mask, and a step of stripping the photoresist using the stripper composition described above.
In the method for stripping the photoresist, the steps of forming the photoresist pattern and patterning the lower film may use a manufacturing process for a conventional device, and a specific production method thereof is not particularly limited.
Meanwhile, examples of the step of stripping the photoresist by using the stripper composition for removing the photoresist are not particularly limited, but for example, the following steps may be used: applying a stripper composition for removing photoresist to a substrate in which a photoresist pattern remains; washing the mixture with an alkaline buffer solution; then washed with ultrapure water and dried. Since the above-described stripper composition exhibits excellent stripping ability and rinsing ability to effectively remove stains on the lower film and ability to remove the native oxide film, it can satisfactorily maintain the surface state of the lower film while effectively removing the photoresist film remaining on the lower film. Thus, subsequent steps may be suitably performed on the patterned lower film to form a device.
Specific examples of the lower film formed on the substrate are not particularly limited, but may include aluminum or aluminum alloy, copper or copper alloy, molybdenum or molybdenum alloy, or a mixture thereof, a composite alloy thereof, a composite laminate thereof, or the like.
The type, composition, or physical characteristics of the photoresist as the target of the stripping method are also not particularly limited, and for example, it may be a photoresist known for a lower film containing aluminum or an aluminum alloy, copper or a copper alloy, molybdenum or a molybdenum alloy, or the like. More specifically, the photoresist may contain a photosensitive resin component such as a novolac resin, a resole resin, or an epoxy resin.
Advantageous effects
According to the present disclosure, a stripper composition for removing photoresist, which suppresses corrosion of a lower metal film during stripping while having excellent stripping ability for photoresist, and has improved photoresist solubility, and a stripping method of photoresist using the same, may be provided.
Drawings
FIG. 1 is a scanning electron microscope (FE-SEM) photograph showing the results of evaluating Ti/Al/Ti cross-sectional damage with stripper compositions for photoresist removal according to examples 1 to 6, 9 and 11 of the present disclosure; and
fig. 2 is a scanning electron microscope (FE-SEM) photograph showing the results of evaluating Cu surface damage with stripper compositions for photoresist removal according to examples 1 to 6, 9 and 11 of the present disclosure.
Detailed Description
Hereinafter, the present disclosure will be described in detail with reference to the following examples. However, these examples are for illustrative purposes only, and the scope of the present disclosure is not limited thereto.
< examples 1 to 16: preparation of stripper composition for removing Photoresist
The components were mixed to prepare the stripper compositions for photoresist removal of examples 1 to 16, respectively, according to the compositions of tables 1 and 2 below. The specific composition of the stripper composition for removing photoresist prepared is described in tables 1 and 2 below.
TABLE 1
TABLE 2
AEE:2- (2-aminoethoxy) ethanol, CAS:929-06-6
MIPA: 1-amino-2-propanol, CAS:78-96-6
MEA: monoethanolamine, CAS:141-43-5
AEEA: aminoethylethanolamine, CAS:111-41-1
N-MEA: n-methylethanolamine, CAS:109-83-1
DEA: diethanolamine, CAS:150-59-9
IME: 1-imidazolidine ethanol, CAS:77215-47-5
HEP: hydroxyethyl-piperazine, CAS:103-76-4
AEP: n-aminoethylpiperazine, CAS:140-31-8
NMF: n-methylformamide, CAS:123-39-7, a boiling point of 182.5 DEG C
NMP: n-methyl-2-pyrrolidone, CAS:872-50-4, boiling point 202 DEG C
NEF: n-ethylformamide, CAS:627-45-2, boiling point 202 ℃ to 204 DEG C
DEF: n, N-diethylformamide, CAS:617-84-5, boiling point 178.3 DEG C
MDG: diethylene glycol methyl ether, CAS:111-77-3
EDG: diethylene glycol monoethyl ether, CAS:111-90-0
BDG: diethylene glycol monobutyl ether, CAS:112-34-5
DGtB: diethylene glycol mono-t-butyl ether, CAS:110-09-8
DIW: deionized water
Corrosion inhibitor 1:2,2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol, CAS:88477-37-6
Corrosion inhibitor 2:4,5,6, 7-tetrahydro-1H-benzotriazole, CAS:6789-99-7
Corrosion inhibitor 3: 2-mercapto-1-methylimidazole, CAS:60-56-0
Comparative examples 1 to 15: preparation of stripper composition for removing Photoresist
According to the compositions of tables 3, 4 and 5, the respective components were mixed to prepare stripper compositions for removing photoresist of comparative examples 1 to 15, respectively. The specific compositions of the stripper composition for removing photoresist prepared above are as described in tables 3, 4 and 5 below.
TABLE 3
TABLE 4
TABLE 5
< experimental example: measurement of physical Properties of stripper composition for removing Photoresist obtained in examples and comparative examples-
300g of each of the compositions of tables 1 to 5 was prepared in a 500ml beaker, stirred at 500rpm on a hot plate, and heated to 60℃to prepare a chemical solution (stripper composition).
Physical properties of the prepared chemical solutions were measured by the following methods, and the results are shown in each table.
1. Evaluation of Peel ability
After the photo process on a-Si, a substrate having a photoresist pattern with a size of 3cm×3cm was prepared and hard baked at 170℃for 20 minutes.
The substrate was immersed in the prepared chemical solution at 60 c every 30 seconds, and then taken out and washed in three stages of deionized water for 30 seconds. Deionized water was dried using an air gun.
The prepared samples were analyzed by optical microscopy and the point in time when the photoresist residue disappeared was evaluated as the stripping time.
The stripping ability of the stripper compositions of examples and comparative examples was evaluated in the same manner as above, and the results are shown in the following tables 6 and 7.
TABLE 6
TABLE 7
As shown in tables 6 and 7, it can be confirmed that the stripper composition of the examples contains a primary or secondary chain amine compound, a cyclic amine compound and an amide compound having a boiling point of 180 ℃ or more in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms in predetermined amounts, which exhibit excellent stripping ability as compared with the stripper composition of the comparative examples.
Furthermore, from table 7, it can be determined that the stripper compositions of comparative examples 1 to 6 containing one type of primary or secondary chain amine compound or one type of cyclic amine compound exhibit significantly reduced stripping ability compared to the examples, so that there is a risk of post-treatment defects in the photoresist residue.
Furthermore, the stripper composition of comparative example 15, which contained an excess of imidazolyl-4-ethanol, which is a cyclic amine, exhibited significantly reduced stripping ability compared to the examples, compared to (2-aminoethoxy) -1-ethanol, which is a chain amine, so that there was a risk of post-treatment defects in the photoresist residue.
Evaluation of Ti/Al/Ti section failure
After the photo process on the Ti/Al/Ti, a substrate having a photoresist pattern with a size of 3cm×3cm was prepared, and the substrate was immersed in the prepared chemical solution at 60 ℃ for 120 seconds. The substrate was removed, washed in three stages of deionized water for 30 seconds, and the deionized water was dried using an air gun.
After repeating the above procedure three times, the Ti/Al/Ti cross-section was analyzed for damage by FE-SEM.
When the Al layer has a damage as compared to the sample not subjected to the chemical treatment, the presence or absence of the cross-sectional damage is evaluated as having the cross-sectional damage.
The Ti/Al/Ti cross-section damage of the stripper compositions of the examples and comparative examples was evaluated in the same manner as above, and the results are shown in table 8, table 9 and fig. 1 below.
TABLE 8
TABLE 9
As shown in table 8, table 9 and fig. 1, no damage to the Ti/Al/Ti section was observed in the examples of the present disclosure, but damage to the Ti/Al/Ti section was observed in comparative examples 1 to 3. From this, it can be determined that the stripping agent composition of the present disclosure comprising a primary or secondary chain amine compound, a cyclic amine compound, and an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and a boiling point (bp) of 180 ℃ or higher in a predetermined amount minimizes damage to metals.
3. Evaluation of copper surface damage
A substrate having Cu deposited on the front surface thereof in a size of 3cm×3cm was prepared, and then the substrate was immersed in the prepared chemical solution at 60 ℃ for 120 seconds, and the substrate was taken out and washed in three-stage deionized water for 30 seconds. Deionized water was dried using an air gun.
After repeating the above procedure 3 times, cu surface damage was analyzed by FE-SEM.
The presence or absence of surface damage is assessed as having surface damage when there is a morphological change compared to the sample that has not been chemically treated.
Cu surface damage of the stripper compositions of examples and comparative examples was evaluated in the same manner as above, and the results are shown in the following table 10, table 11 and fig. 2.
TABLE 10
TABLE 11
As shown in table 10, table 11, and fig. 2, no damage to the Cu surface was observed in the examples of the present disclosure, but damage to the Cu surface was observed in comparative examples 1 to 3. From this, it can be determined that the stripping agent composition of the present disclosure comprising a primary or secondary chain amine compound, a cyclic amine compound, and an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and a boiling point (bp) of 180 ℃ or higher in a predetermined amount minimizes damage to metals.
4. Evaluation of photoresist solubility
The photoresist stock solution (CT-3813, manufactured by COTEM) was oven-baked at 150 ℃ for 4 hours to prepare 3% photoresist powder (PR powder).
PR powder was dissolved in the prepared chemical solution at 60℃for 1 hour, and then the dissolved chemical solution was vacuum-filtered through a filter having a pore size of 1 μm and a diameter of 90 mm.
After drying in an oven at 100 ℃ for 1 hour, the weight of the filter was measured, compared with the weight before filtration to calculate PR solubility, and the results are shown in table 12 below.
PR solubility = (weight of filter before filtration/weight of filter after drying) ×100%)
TABLE 12
| Category(s) | Example 7 | Example 11 | Example 12 | Example 14 | Comparative example 7 | Comparative example 8 | Comparative example 15 |
| PR solubility | 96.76％ | 98.85％ | 98.54％ | 98.47％ | 92.37％ | 91.89％ | 94.08％ |
As shown in table 12, the examples of the present disclosure all exhibited a solubility of 95% or more, but the comparative examples exhibited a solubility of less than 95%.
The higher the solubility of the photoresist, the lower the likelihood of photoresist residue remaining on the substrate after the stripping process. Thus, the stripper composition of the present disclosure comprising a primary or secondary chain amine compound, a cyclic amine compound and an amide compound in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and a boiling point (bp) of 180 ℃ or higher in a predetermined content is more economical and effective compared to the comparative example.
5. Evaluation of contact angle
A substrate having Cu deposited on the front surface thereof in a size of 3cm×3cm was prepared, and then immersed in the prepared chemical solution at 60 ℃ for 120 seconds, taken out, and washed in three-stage deionized water for 30 seconds. Deionized water was dried using an air gun.
Mu.l of deionized water (DIW) was dropped on the prepared sample, and then the angle between the sample and deionized water was measured. The left and right angles of the samples were measured and their average value calculated using the apparatus DSA100 from KRUSE. The degree of hydrophilization of a surface is evaluated by an average value of contact angles, and it means that the lower the contact angle value, the stronger the degree of hydrophilization, and thus the degree of residual organic matter on the surface.
The contact angles of the stripper compositions of examples and comparative examples were evaluated in the same manner as above, and the results are shown in table 13 below.
TABLE 13
As shown in table 13, it can be determined that the stripper composition of the examples of the present disclosure exhibited a contact angle distribution of 54 ° ± 2 °, and the comparative examples exhibited a value significantly deviating from 54 °. From this, it was confirmed that the degree of surface hydrophilization was greatly affected by the content of the amide compound in the stripper composition.
In particular, in the case of comparative example 15, the hydrophilic surfactant remained in the stripper composition, and the contact angle was greatly reduced to 42 °, which may cause a problem of a change in contact resistance of the metal.
Claims (16)
1. A stripper composition for removing photoresist comprising:
primary or secondary chain amine compounds;
a cyclic amine compound;
amide compounds in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms and having a boiling point of 180 ℃ or higher;
a protic solvent; and
a corrosion inhibitor is used in the formulation of a corrosion inhibitor,
wherein the amide compound having a boiling point of 180 ℃ or more in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms is contained in an amount of 60 to 90% by weight with respect to the total weight of the stripper composition, and
wherein the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is from 100:1 to 1:1.
2. The stripper composition for removing photoresist according to claim 1, wherein:
the amide compounds having a boiling point of 180 ℃ or more in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms include compounds of the following chemical formula 1:
[ chemical formula 1]
Wherein, in the chemical formula 1,
R 1 is hydrogen, methyl, ethyl or propyl,
R 2 is a methyl group or an ethyl group,
R 3 is hydrogen or a linear or branched alkyl radical having 1 to 5 carbon atoms, and
R 1 and R is 3 Optionally in combination with each other to form a ring.
3. The stripper composition for removing photoresist according to claim 1, wherein:
the amide compound having a boiling point of 180 ℃ or more in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms includes at least one selected from the group consisting of: n-methylformamide, N-ethylformamide, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.
4. The stripper composition for removing photoresist according to claim 1, wherein:
the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is from 80:1 to 1.5:1.
5. The stripper composition for removing photoresist according to claim 1, wherein:
the total content of the primary or secondary chain amine compound and the cyclic amine compound is contained in an amount of 1 to 20% by weight relative to the total weight of the stripper composition.
6. The stripper composition for removing photoresist according to claim 1, wherein:
the primary or secondary chain amine compound includes at least one selected from the group consisting of: 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, monoethanolamine, aminoethylethanolamine, N-methylethanolamine and diethanolamine.
7. The stripper composition for removing photoresist according to claim 1, wherein:
the cyclic amine compound comprises an intramolecular tertiary amine structure.
8. The stripper composition for removing photoresist according to claim 1, wherein:
the cyclic amine compound is a saturated amine compound.
9. The stripper composition for removing photoresist according to claim 1, wherein:
the cyclic amine compound includes at least one selected from the group consisting of: 1-imidazolidineethanol, 1- (2-hydroxyethyl) piperazine and N- (2-aminoethyl) piperazine.
10. The stripper composition for removing photoresist according to claim 1, wherein:
the protic solvent comprises an alkylene glycol monoalkyl ether-based compound.
11. The stripper composition for removing photoresist according to claim 1, wherein:
the corrosion inhibitor includes at least one selected from the group consisting of: triazole-based compounds and imidazole-based compounds.
12. The stripper composition for removing photoresist according to claim 11, wherein:
the triazole-based compound includes at least one selected from the group consisting of: 2,2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol and 4,5,6, 7-tetrahydro-1H-benzotriazol.
13. The stripper composition for removing photoresist according to claim 11, wherein:
the imidazole-based compound includes 2-mercapto-1-methylimidazole.
14. The stripper composition for removing photoresist according to claim 1, comprising: relative to the total weight of the stripper composition,
1 to 20% by weight of a primary or secondary chain amine compound and a cyclic amine compound;
60 to 90% by weight of an amide compound having a boiling point of 180 ℃ or more in which nitrogen is substituted with one or two linear or branched alkyl groups having 1 to 5 carbon atoms;
0.01 to 10 wt% of a corrosion inhibitor; and
the remaining amount of protic solvent.
15. The stripper composition for removing photoresist according to claim 1, wherein:
the stripper composition includes a silicone-based nonionic surfactant in an amount of less than 0.001 wt% based on the total weight of the stripper composition.
16. A method for stripping photoresist comprising the steps of:
forming a photoresist pattern on a substrate having a lower film formed therein;
patterning the lower film with the photoresist pattern; and
the photoresist is stripped using the stripper composition for removing photoresist according to claim 1.
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| KR1020220078924A KR20230075339A (en) | 2021-11-22 | 2022-06-28 | Stripper composition for removing photoresist and stripping method of photoresist using the same |
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| US5648324A (en) * | 1996-01-23 | 1997-07-15 | Ocg Microelectronic Materials, Inc. | Photoresist stripping composition |
| KR20060024478A (en) * | 2004-09-13 | 2006-03-17 | 주식회사 동진쎄미켐 | Composition for removing a photoresist |
| US20060116313A1 (en) * | 2004-11-30 | 2006-06-01 | Denise Geitz | Compositions comprising tannic acid as corrosion inhibitor |
| US7888302B2 (en) * | 2005-02-03 | 2011-02-15 | Air Products And Chemicals, Inc. | Aqueous based residue removers comprising fluoride |
| TW200633046A (en) * | 2005-02-14 | 2006-09-16 | Robert J Small | Semiconductor cleaning |
| JP5236217B2 (en) * | 2006-06-22 | 2013-07-17 | 東進セミケム株式会社 | Resist removing composition |
| US8361237B2 (en) * | 2008-12-17 | 2013-01-29 | Air Products And Chemicals, Inc. | Wet clean compositions for CoWP and porous dielectrics |
| JP5678616B2 (en) * | 2010-12-02 | 2015-03-04 | 東ソー株式会社 | Resist stripper and stripping method using the same |
| KR101595977B1 (en) * | 2013-03-07 | 2016-02-19 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping mthod of photoresist using the same |
| KR101586453B1 (en) * | 2014-08-20 | 2016-01-21 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping method of photoresist using the same |
| KR101707155B1 (en) * | 2014-08-20 | 2017-02-27 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping method of photoresist using the same |
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