CN103365121B - Resist stripping composition and the method for removing resist using the resist stripping composition - Google Patents
Resist stripping composition and the method for removing resist using the resist stripping composition Download PDFInfo
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Abstract
The present invention discloses a kind of resist stripping composition, including：(a) penta cycle compound of hydroxy dioxetane that chemical formula 1 indicates；And (b) alkali compounds.
Description
Technical field
The method for removing resist the present invention relates to resist stripping composition and using the resist stripping composition.
More particularly it relates to a kind of resist stripping composition and the side using resist stripping composition stripping resist
Method, the resist pattern and etching which can be effectively removed during flat-panel monitor production process
Residue does not damage aluminum wiring and/or copper wiring, non-volatile in stripping process, and is not remained after stripping process.
Background technology
Recently, with the increase in demand to realizing high-resolution flat-panel monitor, to the pixel of increase per unit area
Number has carried out lasting effort.According to this trend, the width for reducing wiring is needed, and respond this demand, introduced
Dry method etch technology, and process conditions are increasingly stringenter.
In addition, in flat-panel monitor when becoming large-sized, need to increase signal speed in the wiring, then than the electricity of aluminium
The low copper of resistance rate is used particularly as wiring material.Respond the trend, it is similarly desirable to increase anti-in the stripping technology of removal resist
Lose the performance of agent stripper.
In particular it is required that with the etch residue that high level removal generates after dry method etch technology, and it is anti-with high level
The only corrosion of metal wiring.Patience of the copper to the patience of corrosion and aluminium to corrosion is especially needed, and in order to ensure price is competing
Strive power and business efficiency, it is also desirable to increase the number etc. of pending substrate.
It has developed new technology and has responded the demand.For example, Korean unexamined patent application publication number 2011-
0004341 discloses a kind of composition (pH7) including acetal or ketal, water, polyalcohol, pH adjusting agent and preservative.
The technology is characterized in that：Hydroxide, TMAH, KOH etc. are used as pH adjusting agent, and water-insoluble acetal
Or water-soluble acetal (dioxolanes class) is used as solvent.
However, problem is：Water-insoluble acetal will produce residual with higher boiling and during flushing process due to it；
Water-soluble acetal (dioxolanes class) is volatilized since it has 100 DEG C or lower boiling point during stripping process, to draw
Play process loss；And due to hydroxide, TMAH, KOH etc. are used as pH adjusting agent, in order to obtain enough anti-corrosions effect
Fruit needs a large amount of preservative.
Korean unexamined patent application publication number：2011-0004341
Invention content
Therefore, the present invention is had been devised by solve the above problems, and the purpose of the present invention is to provide a kind of resist stripping
The side of resist is removed from composition (resist stripper composition) and using the resist stripping composition
Method, the resist stripping composition can be effectively removed resist pattern, dry method erosion during flat-panel monitor production process
Residue and wet etching residue are carved, can be effectively prevented to the corrosion including aluminium and/or the metal wiring of copper, in stripping process
Period is non-volatile, and is not remained after stripping process.
To achieve the goals above, one aspect of the present invention provides a kind of resist stripping composition, including：(a)
Penta cycle compound of hydroxy dioxetane that following chemical formula 1s indicate；And (b) alkali compounds,
[chemical formula 1]
Wherein R1 and R2 respectively stands alone as alkenyl, 1 to 5 carbon of hydrogen, the alkyl of 1 to 5 carbon atom, 2 to 5 carbon atoms
The hydroxyalkyl or phenyl of atom, and R3 is the alkylidene of 1 to 4 carbon atom, the alkenylene of 2 to 5 carbon atoms or 1 to 5
The hydroxy alkylidene of carbon atom.
The resist stripping composition may include that the cyclisation of hydroxy dioxetane penta of 80 to 99.9wt% above-mentioned chemical formula 1 is closed
Object and 0.1 to 20wt% alkali compounds.
The resist stripping composition can further comprise (c) preservative.
The resist stripping composition may include penta ring of hydroxy dioxetane of 77 to 99.89wt% (a) above-mentioned chemical formula 1
Compound, 0.1 to 20wt% (b) alkali compounds and 0.01 to 3wt% (c) preservative.
(a) penta cycle compound of hydroxy dioxetane of above-mentioned chemical formula 1 can be selected from by 4- methylols -1,3-dioxolane,
4- methylols -2,2- dimethyl -1,3-dioxolane, 4- ethoxys -2,2- dimethyl -1,3-dioxolane, hydroxypropyl -2 4-,
2- dimethyl -1,3-dioxolane, 4- hydroxyls butyl -2,2- dimethyl -1,3-dioxolane, 4- methylols -2,2- diethyl -1,
One kind in the group that 3- dioxolanes and 4- methylol -2- methyl -2- ethyls -1,3-dioxolane are formed or two kinds or
Mixture more than two kinds.
(b) alkali compounds is selected from by KOH, NaOH, TMAH (tetramethylammonium hydroxide), TEAH (tetraethyl hydroxides
Ammonium), a kind of or two kinds or the mixture more than two kinds in the group that is formed of carbonate, phosphate, ammonia and amine..
(c) preservative be selected from by succinamide ester, malic acid carboxylic acid amide esters, maleic acid ester, amides ester,
Oxalic acid amide esters, malonic acid carboxylic acid amide esters, glutaramide ester, amide ester, lactamide ester, citric mide ester, winestone
Sour carboxylic acid amide esters, oxyacetic acid carboxylic acid amide esters, benzoic acid amides ester and uric acid carboxylic acid amide esters；Benzotriazole, tolyl-triazole, methyl toluene base
Triazole, 2,2 '-[[[benzotriazole] methyl] imino group] diethanols, 2,2 '-[[[methyl-1 H- benzotriazole -1- bases] methyl]
Imino group] dimethanol, 2,2 '-[[[ethyl -1H- benzotriazole -1- bases] methyl] imino group] diethanols, 2,2 '-[[[methyl -
1H- benzotriazole -1- bases] methyl] imino group] diethanol, 2,2 '-[[[methyl-1 H- benzotriazole -1- bases] methyl] imido
Base] dicarboxylic acids, 2,2 '-[[[methyl-1 H- benzotriazole -1- bases] methyl] imino group] dimethylamine and 2,2 '-[[amino -1H-
Benzotriazole -1- bases] methyl] imino group] diethanol (2,2 '-[[[amine-1H-benzotriazole-1-yl] methyl]
imino]bisethanol)；1,2- 1,4-benzoquinone, Isosorbide-5-Nitrae -1,4-benzoquinone, 1,4-naphthoquinone and anthraquinone；And catechol, pyrogallol,
In the group that gallicin, propylgallate, lauryl gallate, octyl gallate and gallic acid are formed
One kind or two kinds or the mixture more than two kinds.
The resist stripping composition can further comprise in (d) water soluble polar solvent and (e) deionized water at least
It is a kind of.
The resist stripping composition may include that the hydroxy dioxetane penta of 1 to 99.9wt% (a) above-mentioned chemical formula 1 is cyclized
Close object, 0.1 to 20wt% (b) alkali compounds and in (d) water soluble polar solvent and (e) deionized water at least
A kind of surplus.
The resist stripping composition may include penta ring of hydroxy dioxetane of 1 to 99.89wt% (a) above-mentioned chemical formula 1
Compound, 0.1 to 20wt% (b) alkali compounds, 0.01 to 3wt% (c) preservative and be selected from (d) watersoluble polar
The balanced agent of at least one of solvent and (e) deionized water.
(d) water soluble polar solvent can be proton polar solvent in addition to polyalcohol, aprotic polar solvent or they
Mixture.
Another aspect of the present invention provides a kind of method of stripping resist, includes the following steps：(I) in FPD
Conductive metal deposition film on device substrate；(II) resist film is formed on the conductive metal film；(III) institute is selectively exposed
State resist film；(IV) the exposed resist film is made to be developed to resist pattern；(V) the resist figure is used
Case is as conductive metal film described in mask etch；And (VI) is removed using the resist stripping composition from the substrate
It is denaturalized by the formation of the resist pattern and the etching of the conductive metal film and cured resist.
An additional aspect of the present invention provides a kind of method manufacturing the tablet for display, including resist is used to shell
The step of resist being removed from composition from flat panel substrate.
An additional aspect of the present invention is to provide a kind of method of manufacture flat-panel monitor, including uses resist stripping group
Close the step of object removes resist from flat panel substrate.
An additional aspect of the present invention provides a kind of tablet for display manufactured according to this method.
An additional aspect of the present invention provides a kind of flat-panel monitor manufactured according to this method.
Specific implementation mode
Hereinafter, will be described in the component of the present invention.
One aspect of the present invention provides a kind of resist stripping composition, including：(a) following chemical formula 1s indicate
Penta cycle compound of hydroxy dioxetane；And (b) alkali compounds.
The resist stripping composition can further comprise (c) preservative.
The resist stripping composition can further comprise in (d) water soluble polar solvent and (e) deionized water at least
It is a kind of.
(a) penta cycle compound of hydroxy dioxetane that chemical formula 1 indicates
The resist stripping composition of the present invention includes penta cycle compound of hydroxy dioxetane that following chemical formula 1 indicates, should
Penta cycle compound of hydroxy dioxetane is water-soluble solvent：
[chemical formula 1]
Wherein R1 and R2 respectively stands alone as alkenyl, 1 to 5 carbon of hydrogen, the alkyl of 1 to 5 carbon atom, 2 to 5 carbon atoms
The hydroxyalkyl or phenyl of atom, and R3 is the alkylidene of 1 to 4 carbon atom, the alkenylene of 2 to 5 carbon atoms or 1 to 5
The hydroxy alkylidene of carbon atom.
The example of penta cycle compound of hydroxy dioxetane may include：4- methylols -1,3-dioxolane, 4- methylols -2,2- bis-
Methyl-1,3- dioxolanes, 4- ethoxys -2,2- dimethyl -1,3-dioxolane, 4- hydroxypropyls -2,2- dimethyl -1,3- bis-
Butyl oxide link, 4- hydroxyls butyl -2,2- dimethyl -1,3-dioxolane, 4- methylols -2,2- diethyl -1,3-dioxolane and 4-
Methylol -2- methyl -2- ethyls -1,3-dioxolane.They can be used alone or mixture with two kinds or more than two kinds
Form uses.
Penta cycle compound of hydroxy dioxetane is water-soluble solvent for dissolving imaging polymers, the flushing after stripping
It is not remained on substrate during process, and there is 100 DEG C or higher boiling point, so as to prevent resist stripping composition
Volatilization and the loss during stripping process.
Total amount based on composition, it may include 1 to 99.9wt%, preferably 10 to the 98wt% hydroxy dioxetane penta cyclisation is closed
Object.
In the acetal solvent for conventional resist stripping composition, the tetramethyl of 100 DEG C or higher boiling point is all had
Oxygroup propane, tetramethoxy ethane, phenylacetaldehyde dimethyl acetal, chloroacetaldehyde dimethylacetal, chloroacetaldehyde diethyl acetal etc. are non-aqueous
Property, and metaformaldehyde has compared with low-solubility in water.Therefore, the problem of these acetal solvents, is：After stripping process
Flushing process during, itself residual of agent stripping solution against corrosion and when composition contains water, is issued in long-time storage
Generating layer detaches, and therefore, it is difficult to ensure long-time stability.
Meanwhile it is water-soluble and with lower boiling point 1,3-dioxolane the problem of be：In room temperature or it is higher than room
Under temperature, 1,3-dioxolane is volatilized and is lost during stripping process, and therefore resist stripping composition has to last for mending
It gives.
(b) alkali compounds
The example of alkali compounds may include：KOH, NaOH, TMAH (tetramethylammonium hydroxide), TEAH (tetraethyl hydrogen-oxygens
Change ammonium), carbonate, phosphate, ammonia and amine.They can be used alone or the mixture by two kinds or more than two kinds in the form of make
With.
The example of amine may include：Such as methylamine, ethamine, isopropylamine, n-butylamine, sec-butylamine, isobutyl amine, tert-butylamine, amylamine
Equal primary amine；Such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutyl amine, di-iso-butylmanice, methyl ethyl-amine, methyl propylamine, first
The secondary amine such as base isopropylamine, methylbutylamine, methyl tert-butyl amine；Such as diethyl hydroxylamine, trimethylamine, triethylamine, tripropyl amine (TPA), three fourths
The tertiary amines such as amine, triamylamine, dimethyl amine, methyl ethyl-amine, methyl-di-n-propylamine；Such as choline, monoethanolamine, diethanol amine, three
Ethanol amine, single Propanolamine, 2- ethylaminoethanols, 2- (ethylamino) ethyl alcohol, 2- (methylamino) ethyl alcohol, N methyldiethanol amine,
N, N- dimethylethanolamine, N, N- DEAE diethylaminoethanols, 2- (2- aminoethylaminos) -1- ethyl alcohol, 1- amino -2- propyl alcohol,
The alkanolamines such as 2- amino -1- propyl alcohol, 3- amino -1- propyl alcohol, 4 amino-n-butyl alcohol, two butanolamines；Such as (butoxymethyl) two
Ethamine, (methoxy) diethylamine, (methoxy) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl)
Dimethylamine, (methoxy) diethanol amine, (hydroxy ethoxy methyl) diethylamine, methyl (methoxy) aminoethane, first
The alcoxyls amine such as base (methoxy) ethylaminoethanol, methyl (butoxymethyl) ethylaminoethanol, 2- (2 amino ethoxy) ethyl alcohol；
And such as 1- (2- ethoxys) piperazine, 1- (2- amino-ethyls) piperazine, 1- (2- ethoxys) methyl piperazine, N- (3- aminopropans
Base) morpholine, 2- methyl piperazines, 1- methyl piperazines, 1- amino -4- methyl piperazines, 1- benzyl diethylenediamines, 1-php, N- methyl
The cyclammonium such as morpholine, 4- ethyl morpholines, N- N-formyl morpholine Ns, N- (2- ethoxys) morpholine, N- (3- hydroxypropyls) morpholine.
Alkali compounds penetrates into several technique items in dry etching or wet etching, ashing, ion implantation technology etc.
Under part in the polymer substrate of denaturation or crosslinked resist, with the key for being broken intramolecular and intermolecular key.In addition, alkalization
It closes and forms vacancy in the structural vulnerable area of resist of the object on remaining in substrate so that resist is converted to amorphous gather
Object gel block is closed, so as to be readily removable the resist being attached on substrate.
Total amount based on composition, it may include 0.1 to 20wt%, preferably 1 to 15wt% alkali compounds.Work as alkalization
When closing the amount of object less than 0.1%, the problem is that：Resist cannot be easily peeled off.In addition, the amount when alkali compounds is more
When 20%, the problem is that：The metal wiring fast erosion made of aluminium, aluminium alloy, copper or copper alloy.
(c) preservative
The example of preservative may include：Such as succinamide ester, malic acid carboxylic acid amide esters, maleic acid ester, fumaric acid
Carboxylic acid amide esters, oxalic acid amide esters, malonic acid carboxylic acid amide esters, glutaramide ester, amide ester, lactamide ester, citric mide
The organic acid amides esters such as ester, tartaric acid carboxylic acid amide esters, oxyacetic acid carboxylic acid amide esters, benzoic acid amides ester, uric acid carboxylic acid amide esters；Such as benzo three
Azoles, tolyl-triazole, methyl toluene base triazole, 2,2 '-[[[benzotriazole] methyl] imino group] diethanols, 2,2 '-[[[first
Base -1H- benzotriazole -1- bases] methyl] imino group] dimethanol, 2,2 '-[[[ethyl -1H- benzotriazole -1- bases] methyl] is sub-
Amino] diethanol, 2,2 '-[[[methyl-1 H- benzotriazole -1- bases] methyl] imino group] diethanols, 2,2 '-[[[methyl-1 H-
Benzotriazole -1- bases] methyl] imino group] dicarboxylic acids, 2,2 '-[[[methyl-1 H- benzotriazole -1- bases] methyl] imino groups] two
Methylamine and 2,2 '-[[amino -1H- benzotriazole -1- bases] methyl] imino groups] azole compounds such as diethanol；Such as 1,2-
The quinines such as 1,4-benzoquinone, Isosorbide-5-Nitrae -1,4-benzoquinone, 1,4-naphthoquinone, anthraquinone；Such as catechol, nutgall methyl esters, does not have pyrogallol
The alkyl gallic acid compound such as propyl galate, lauryl gallate, octyl gallate and gallic acid.They can
It is used in the form of exclusive use or the mixture by two kinds or more than two kinds.
There is higher solubility in water or in polar solvent due to each above compound, it will not as preservative
It remains on a surface of a substrate, there is excellent antiseptic property to the metal wiring including aluminium and/or copper, and will not cause against corrosion
The color change of agent stripping composition.
Total amount based on composition, it may include 0.01 to 3wt%, preferably 0.01 to 2wt% preservative.When preservative
When amount is less than 0.01%, the metal wiring made of aluminium, aluminium alloy, copper or copper alloy can be sent out in stripping or in DI flushing processes
Raw corrosion.In addition, when the amount of preservative is more than 3wt%, resist stripping composition is adsorbed on the surface of metal wiring, to
Cause the secondary pollution of metal wiring and deteriorates the fissility of composition.
The resist stripping composition can further comprise in (d) water soluble polar solvent and (e) deionized water at least
It is a kind of.
(d) water soluble polar solvent
The water soluble polar solvent may include proton polar solvent in addition to the polyol and aprotic polar solvent.They can
It is used alone or uses as a mixture.
The example of proton polar solvent may include：Such as ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol Dan Yi
Propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, two
Ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol
Single-butyl ether, polyethylene glycol monomethyl ether, polyethylene glycol single-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, three
The alkylene glycol monoalkyl ethers class such as propylene glycol monomethyl ether；And tetrahydrofurfuryl alcohol class.They can be used alone or with mixture
Form use.
The example of aprotic polar solvent may include：The pyrroles such as N-Methyl pyrrolidone (NMP), N- ethyl pyrrolidones
Pyrrolidone compound；Such as imidazolidinone compounds such as 1,3-Dimethyl-2-imidazolidinone, 1,3- dipropyl -2- imidazolones；
The lactone compounds such as gamma-butyrolacton；The sulfoxide compounds such as dimethyl sulfoxide (DMSO), sulfolane；Such as tricresyl phosphate second
The phosphate compounds such as ester, tributyl phosphate；The carbonate products such as dimethyl carbonate, ethylene carbonate；And such as
Formamide, N-METHYLFORMAMIDE, n,N-Dimethylformamide, acetamide, N- methylacetamides, n,N-dimethylacetamide, N-
(2- ethoxys) acetamide, 3- methoxyl groups-N, N- dimethylpropionamide, 3- (2- ethyl hexyl oxies)-N, N- dimethylpropionamides,
The amide compounds such as 3- butoxy-N, N- dimethylpropionamide.They can be used alone or the mixing with two kinds or more than two kinds
The form of object uses.
Imaging polymers of the water soluble polar solvent together with penta cycle compound of hydroxy dioxetane for dissolving gelation.
In addition, water-soluble solvent enable to it is against corrosion using being readily removable during the flushing process of deionized water after removing resist
Agent stripping composition, to farthest reduce adsorbing and gluing again again for resist stripping composition and the resist of dissolving
It is attached.
The water soluble polar solvent can have not high also not low boiling point, to show fissility appropriate, and can be with
The form of mixture uses.The water soluble polar solvent is otherwise used in stripping process.The water soluble polar solvent amount can be, but
It is not particularly limited to 5 to 60wt%, preferably 10 to 50wt%.
(e) deionized water
Deionized water activated alkaline compound, and can be fast during flushing process to increase the detachment rate of resist
Speed and fully removal remain in organic pollution and resist stripping composition on substrate.
The amount of total weight based on composition, deionized water can be 70wt% or less, preferably 45wt% or less.When going
When the amount of ionized water is higher than 70%, the dissolved efficiency of resist reduces, to reduce the number for the substrate layer that can be handled, and
When substrate immerses resist stripping composition for a long time, corrodible metal wiring.
The resist stripping composition of the present invention may include the hydroxyl two of 80 to 99.9wt% (a) above-mentioned chemical formula 1
Butyl oxide link compound and 0.1 to 20wt% (b) alkali compounds.
In addition, the resist stripping composition of the present invention may include 77 to 99.89wt% (a) above-mentioned chemical formula 1
Penta cycle compound of hydroxy dioxetane, 0.1 to 20wt% (b) alkali compounds and 0.01 to 3wt% (c) preservative.
In addition, the resist stripping composition of the present invention may include the hydroxyl of 1 to 99.9wt% (a) above-mentioned chemical formula 1
Base dioxolane compound, 0.1 to 20wt% (b) alkali compounds and selected from (d) water soluble polar solvent and (e) go from
The surplus of at least one of sub- water.
In addition, the resist stripping composition of the present invention may include the hydroxyl of 1 to 99.89wt% (a) above-mentioned chemical formula 1
Base dioxolane compound, 0.1 to 20wt% (b) alkali compounds, 0.01 to 3wt% (c) preservative and be selected from (d)
The surplus of at least one of water soluble polar solvent and (e) deionized water.
In addition, the resist stripping composition of the present invention may include the hydroxyl of 10 to 98wt% (a) above-mentioned chemical formula 1
Dioxolane compound, 0.1 to 20wt% (b) alkali compounds, 0.01 to 3wt% (c) preservative and be selected from (d) water
The surplus of at least one of soluble polar solvent and (e) deionized water.
The resist stripping composition of the present invention can be prepared by mixing above compound with predetermined ratio.Mixed side
Method is not to be particularly limited to, and without limitation, various common known methods can be used.
The method of stripping resist according to the present invention includes the following steps：(I) it deposits and leads on flat display substrate
Electric metal film；(II) resist film is formed on the conductive metal film；(III) resist film is selectively exposed；
(IV) exposed resist film is made to be developed to resist pattern；(V) use the resist pattern as mask etch
The conductive metal film；And (VI) is removed from the substrate by described against corrosion using the resist stripping composition of the present invention
The formation of agent pattern and the etching of the conductive metal film and be denaturalized and cured resist.
In addition, the method for stripping resist according to the present invention may include the following steps：It is not carrying out utilizing mask shape
In the case of exposing resist film at pattern formation resist pattern, dry etch process or chemically mechanical polishing are carried out
(CMP)；Exposed resist film is removed using the resist stripping composition of the present invention.
In the method for stripping resist, the shape of resist film can be carried out by well known common method in related field
At, exposure, development, etching and podzolic process.
The type of resist includes anode and cathode g- rays, i- rays and far ultraviolet (FUV) resist, electron beam
Resist, X-ray resist, ion beam resist, photoresist etc..The resist stripping composition of the present invention is effectively
It is applied in the photoresist including light-sensitive compound, the light-sensitive compound is substantially by novolak phenolics and diazonium
Naphthoquinones forms.
For removal denaturation and the resist of cured resist and dry etching residue from flat display substrate
There is the substrate for being coated with resist to immerse in stripping solution, or spray the method for stripping solution on substrate for method.At this
In the case of, the physical treatments such as ultrasonic irradiation, brush rolling (brush rolling) and rotation can be used in combination with the above method.
After stripping solution processing, the stripping solution remained on substrate can be removed by cleaning process.In addition to water or isopropanol generation
Outside for stripping solution, the cleaning process is identical as stripping process.
The method that can carry out stripping resist using dipping, spraying or combination thereof.When by dipping, spraying or they
Combination stripping resist when, can be at 15 to 100 DEG C, preferably 30 to 70 DEG C of temperature and 30 seconds to 40 minutes, preferably 1 to 20
The stripping of resist is carried out under conditions of the dipping or spray time of minute.However, these stripping conditions are not strictly to apply
, those skilled in the art can be easy to carry out modification.When the application resist stripping group on the substrate coated with resist
When closing the temperature of object less than 15 DEG C, the time needed for removal denaturation or cured resist film becomes very long.In addition, when applying
When being covered with the temperature for applying resist stripping composition on the substrate of resist higher than 100 DEG C, the bottom of resist film can be damaged,
And it is difficult to handle resist stripping composition.
Resist stripping composition according to the present invention and the side that resist is removed using the resist stripping composition
Method may be used to remove under etching gas, high temperature denaturation and cured resist and etch residue and common against corrosion for removing
Agent.In addition, resist stripping composition according to the present invention and the side using resist stripping composition stripping resist
The advantages of method, is：It is excellent to the corrosion resistance including aluminium or the metal wiring of copper.
Meanwhile the present invention provides a kind of method manufacturing the tablet for display, includes the following steps：Use the present invention
Resist stripping composition from flat panel substrate remove resist the step of.
In addition, the present invention provides a kind of method of manufacture flat-panel monitor, include the following steps：Use the against corrosion of the present invention
The step of agent stripping composition removes resist from flat panel substrate.
Due to completely eliminated resist during manufacture, and include the metal wiring of aluminium and/or copper almost without corruption
Erosion, so the tablet and flat-panel monitor of the display each manufactured by the above method have excellent quality.
In addition, the present invention provides a kind of tablet for display and a kind of flat-panel monitor, each utilizes upper
Resist stripping composition is stated to manufacture.
Hereinafter, the present invention will be described in detail with reference to the following example.However, these embodiments listed are used for illustrating this hair
It is bright, rather than limit the scope of the invention.
<According to the performance evaluation of the resist stripping composition (being free of preservative) of penta cycle compound of hydroxy dioxetane>
Embodiment 1 to 10 and comparative example 1 to 3：The preparation of resist stripping composition
Resist stripping composition is prepared by mixing the ingredient provided in the following table 1.
[table 1]
(unit：Wt%)
HMDO：4- methylols -1,3-dioxolane
HMDMDO：4- methylols -2,2- dimethyl -1,3-dioxolane
DO：1,3-dioxolane
AEE：2- (2- aminoethylaminos) -1- ethyl alcohol
MDEA：N methyldiethanol amine
HEP：Hydroxyethyl piperazine
TMAH：Tetramethylammonium hydroxide
NMP：N-Methyl pyrrolidone
THFA：Tetrahydrofurfuryl alcohol
EDG：Diethylene glycol monobutyl ether
<Experimental example 1>The fissility of resist stripping composition is evaluated
In order to evaluate embodiment 1 to 10 and comparative example 1 to 3 resist stripping composition peeling effect, provide and pass through
Metal film (Mo/Al or Cu/Ti) is formed using sputtering on the glass substrate, forms photoresist pattern, and followed by light
Each substrate for causing resist pattern wet etching and dry etching metal film and being formed.Each substrate is immersed often respectively at 50 DEG C
In kind of resist stripping composition 10 minutes to evaluate the fissility of various resist stripping compositions.Hereafter, it is washed with purification
Each substrate is washed 1 minute to remove the resist stripping composition remained on substrate, and will be washed followed by nitrogen
Drying substrates remain in the purified water of washed substrate to completely remove.
The denaturation degrees of each substrate are evaluated using scanning electron microscope (SEM, Hitachi S-4700) and from each
The performance of cured resist and dry etching residue is removed on a substrate.Its result is shown in the following table 2, and wherein ◎ is non-
Chang Hao, zero preferably, and △ is general, and × it is poor.
<Experimental example 2>The volatile quantity of resist stripping composition is evaluated
In order to evaluate volatile quantity of the resist stripping composition during stripping process, the resist of 500g is removed into combination
Object is placed in the beaker of 100mL, and the beaker for putting into resist stripping composition is put into thermostat (50 DEG C) and in phase equality of temperature
Degree is lower to be maintained 12 and 24 hours, and then measures the weight of the remaining resist stripping composition in beaker to measure resist
The volatile quantity (percentage) of stripping composition.Its result is shown in the following table 2.
[table 2]
From upper table 2, it can be determined that：After 12 and 24 hours, each resist stripping combination of comparative example 1 to 3
The volatile quantity of object (do not contain penta cycle compound of hydroxy dioxetane) is 37.2 to 76.3%, but embodiment 1 to 10 each is against corrosion
The volatile quantity of agent stripping composition (containing penta cycle compound of hydroxy dioxetane) is far smaller than each resist stripping of comparative example 1 to 3
Volatile quantity from composition.
<According to the performance evaluation of the resist stripping composition (containing preservative) of penta cycle compound of hydroxy dioxetane>
Embodiment 11 to 20 and comparative example 4 to 6：The preparation of resist stripping composition
Resist stripping composition is prepared by the ingredient mixed in the following table 3.
[table 3]
(unit：Wt%)
HMDO：4- methylols -1,3-dioxolane
HMDMDO：4- methylols -2,2- dimethyl -1,3-dioxolane
DO：1,3-dioxolane
AEE：2- (2- aminoethylaminos) -1- ethyl alcohol
MDEA：N methyldiethanol amine
HEP：Hydroxyethyl piperazine
TMAH：Tetramethylammonium hydroxide
NMP：N-Methyl pyrrolidone
THFA：Tetrahydrofurfuryl alcohol
EDG：Diethylene glycol monobutyl ether
MG：Methyl gallic acid
BTA：Benzotriazole
<Experimental example 3>The fissility of resist stripping composition is evaluated
In order to evaluate embodiment 11 to 20 and comparative example 4 to 6 resist stripping composition peeling effect, provide and pass through
Metal film (Mo/Al or Cu/Ti) is formed using sputtering on the glass substrate, forms photoresist pattern, and followed by light
Each substrate for causing resist pattern wet etching and dry etching metal film to be formed.Each substrate is immersed at 50 DEG C respectively every
In kind of resist stripping composition 10 minutes to evaluate the fissility of various resist stripping compositions.Hereafter, it is washed with purification
Each substrate is washed 1 minute to remove the resist stripping composition remained on substrate, and will be washed followed by nitrogen
Drying substrates remain in the purified water of washed substrate to completely remove.
The denaturation degrees of each substrate are evaluated using scanning electron microscope (SEM, Hitachi S-4700) and from each base
The performance of cured resist and dry etching residue is removed on plate.Its result is shown in the following table 4, and wherein ◎ is very
Good, zero preferably, and △ is general, and × it is poor.
<Experimental example 4>Resist stripping composition evaluates the antiseptic property of metal wiring
The anti-corrosion of resist stripping composition is carried out using the substrate with exposed metal wiring (Mo/Al or Cu/Ti)
The evaluation of performance.The temperature of each resist stripping composition is maintained 50 DEG C, and substrate is then immersed each respectively
In resist stripping composition, washing is then dry.It is evaluated using scanning electron microscope (SEM, Hitachi S-4700) each
The antiseptic property of substrate.Its result is shown in the following table 4, wherein ◎ be it is very good, zero preferably, and △ be general, and × be compared with
Difference.
<Experimental example 5>The volatile quantity of resist stripping composition is evaluated
In order to evaluate volatile quantity of the resist stripping composition during stripping process, the resist of 500g is removed into combination
Object is placed in the beaker of 100mL, and the beaker for putting into resist stripping composition is put into thermostat (50 DEG C) and in phase equality of temperature
Degree is lower to be maintained 12 and 24 hours, and then measures the weight of the remaining resist stripping composition in beaker to measure resist
The volatile quantity (percentage) of stripping composition.Its result is shown in the following table 4.
[table 4]
From upper table 4, it can be determined that：After 12 and 24 hours, the various resists stripping combination of comparative example 1 to 3
The volatile quantity of object (not containing penta cycle compound of hydroxy dioxetane) is 37.2 to 76.3%, but embodiment 1 to 10 is various against corrosion
The volatile quantity of agent stripping composition (containing penta cycle compound of hydroxy dioxetane) is far smaller than each resist stripping of comparative example 1 to 3
Volatile quantity from composition.
As described above, the advantages of resist stripping composition of the present invention, is：The resist stripping composition is in tablet
It can be effectively removed resist pattern and etch residue during the manufacturing process of display, do not damage aluminum wiring and/or copper is matched
Line, it is non-volatile during stripping process, and do not remained after stripping process.
In addition, the advantages of resist stripping composition of the present invention, is：By using non-combustible non-toxic material hydroxyl
Dioxolanes can solve the problems, such as the Environmental Regulation of remover.
Although for illustrative purposes, have been disclosed for the present invention is preferably carried out mode, those skilled in the art
What will be known is：In the case where not abandoning scope and spirit of the present invention disclosed in the appended claims, various repair can be carried out
Change, add and replaces.
Claims (11)
1. a kind of resist stripping composition, including：
Penta cycle compound of hydroxy dioxetane that 80 to 99.9wt% (a) following chemical formula 1s indicate；And
0.1 to 20wt% (b) alkali compounds；
[chemical formula 1]
Wherein R1 and R2 respectively stands alone as alkenyl, 1 to 5 carbon atom of hydrogen, the alkyl of 1 to 5 carbon atom, 2 to 5 carbon atoms
Hydroxyalkyl or phenyl, and the alkenylene or 1 to 5 carbon original that R3 is the alkylidene of 1 to 4 carbon atom, 2 to 5 carbon atoms
The hydroxy alkylidene of son.
2. a kind of resist stripping composition, including：
Penta cycle compound of hydroxy dioxetane of 77 to 99.89wt% (a) following chemical formula 1s；
0.1 to 20wt% (b) described alkali compounds；
[chemical formula 1]
Wherein R1 and R2 respectively stands alone as alkenyl, 1 to 5 carbon atom of hydrogen, the alkyl of 1 to 5 carbon atom, 2 to 5 carbon atoms
Hydroxyalkyl or phenyl, and the alkenylene or 1 to 5 carbon original that R3 is the alkylidene of 1 to 4 carbon atom, 2 to 5 carbon atoms
The hydroxy alkylidene of son；And
Further comprise 0.01 to 3wt% (c) described preservative.
3. resist stripping composition according to claim 1 or 2, wherein the hydroxy dioxetane of (a) above-mentioned chemical formula 1
Penta cycle compound is selected from by 4- methylol -1,3- dioxolanes, 4- methylol -2,2- dimethyl -1,3- dioxolanes, 4- hydroxyls
Ethyl -2,2- dimethyl -1,3- dioxolanes, 4- hydroxypropyl -2,2- dimethyl -1,3- dioxolanes, 4- hydroxyl butyl -2,2- two
Penta ring of methyl-1,3-dioxy, 4- methylol -2,2- diethyl -1,3- dioxolanes and 4- methylol -2- methyl -2- ethyls -
One kind in the group that 1,3-dioxolane is formed or two kinds or the mixture more than two kinds.
4. resist stripping composition according to claim 1 or 2, wherein (b) described alkali compounds be selected from by
KOH, NaOH, TMAH (tetramethylammonium hydroxide), TEAH (tetraethyl ammonium hydroxide), carbonate, phosphate, ammonia and amine institute group
At group in a kind of or two kinds or mixture more than two kinds.
5. resist stripping composition according to claim 2, wherein (c) described preservative is selected from by succinic acid acyl
Amine ester, malic acid carboxylic acid amide esters, maleic acid ester, amides ester, oxalic acid amide esters, malonic acid carboxylic acid amide esters, glutaric acid acyl
Amine ester, amide ester, lactamide ester, citric mide ester, tartaric acid carboxylic acid amide esters, oxyacetic acid carboxylic acid amide esters, benzoic acid amides ester
With uric acid carboxylic acid amide esters；Benzotriazole, tolyl-triazole, methyl toluene base triazole, 2,2 '-[[[benzotriazole] methyl] imino groups]
Diethanol, 2,2 '-[[[methyl-1 H- benzotriazole -1- bases] methyl] imino group] dimethanols, 2,2 '-[[[ethyl -1H- benzos
Triazol-1-yl] methyl] imino group] diethanol, 2,2 '-[[[methyl-1 H- benzotriazole -1- bases] methyl] imino group] diethyls
Alcohol, 2,2 '-[[[methyl-1 H- benzotriazole -1- bases] methyl] imino group] dicarboxylic acids, 2,2 '-[[[methyl-1 H- benzotriazole -
1- yls] methyl] imino group] dimethylamine and 2,2 '-[[amino -1H- benzotriazole -1- bases] methyl] imino groups] diethanol；1,2-
1,4-benzoquinone, 1,4- 1,4-benzoquinone, 1,4- naphthoquinones and anthraquinone；And catechol, pyrogallol, gallicin, gallic acid third
One kind in the group that ester, lauryl gallate, octyl gallate and gallic acid are formed or two kinds or more than two kinds
Mixture.
6. a kind of resist stripping composition, the resist stripping composition include：
Penta cycle compound of hydroxy dioxetane of 1 to 99.9wt% (a) following chemical formula 1s；
0.1 to 20wt% (b) described alkali compounds；
[chemical formula 1]
Wherein R1 and R2 respectively stands alone as alkenyl, 1 to 5 carbon atom of hydrogen, the alkyl of 1 to 5 carbon atom, 2 to 5 carbon atoms
Hydroxyalkyl or phenyl, and the alkenylene or 1 to 5 carbon original that R3 is the alkylidene of 1 to 4 carbon atom, 2 to 5 carbon atoms
The hydroxy alkylidene of son；And
Further comprise at least one of (d) water soluble polar solvent and (e) deionized water of surplus.
7. a kind of resist stripping composition, wherein the resist stripping composition includes
Penta cycle compound of hydroxy dioxetane of 1 to 99.89wt% (a) following chemical formula 1s；
0.1 to 20wt% (b) described alkali compounds；
[chemical formula 1]
Wherein R1 and R2 respectively stands alone as alkenyl, 1 to 5 carbon atom of hydrogen, the alkyl of 1 to 5 carbon atom, 2 to 5 carbon atoms
Hydroxyalkyl or phenyl, and the alkenylene or 1 to 5 carbon original that R3 is the alkylidene of 1 to 4 carbon atom, 2 to 5 carbon atoms
The hydroxy alkylidene of son；And
Further comprise 0.01 to 3wt% (c) preservative；
At least one of (d) water soluble polar solvent and (e) deionized water of surplus.
8. the resist stripping composition described according to claim 6 or 7, wherein (d) described water soluble polar solvent is except more
Proton polar solvent, aprotic polar solvent except first alcohol or their mixture.
9. a kind of method of stripping resist, includes the following steps：
(I) the conductive metal deposition film on flat display substrate；
(II) resist film is formed on the conductive metal film；
(III) resist film is selectively exposed；
(IV) the exposed resist film is made to be developed to resist pattern；
(V) use the resist pattern as conductive metal film described in mask etch；And
(VI) the resist stripping composition described in any one of claim 1 to 8 is used to be removed by described from the substrate
The formation of resist pattern and the etching of the conductive metal film and be denaturalized and cured resist.
It is against corrosion 10. a kind of method of tablet of manufacture for display, including described in any one of using claim 1 to 8
The step of agent stripping composition removes resist from flat panel substrate.
A kind of resist stripping 11. method of manufacture flat-panel monitor, including described in any one of using claim 1 to 8
The step of composition removes resist from flat panel substrate.
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| KR1020120032662A KR101543827B1 (en) | 2012-03-29 | 2012-03-29 | Resist stripper composition and a method of stripping resist using the same |
| KR1020120032663A KR101734593B1 (en) | 2012-03-29 | 2012-03-29 | Resist stripper composition and a method of stripping resist using the same |
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| CN111781808B (en) * | 2015-09-16 | 2024-06-07 | 东友精细化工有限公司 | Resist stripping liquid composition, flat panel display substrate and manufacturing method thereof |
| KR102040068B1 (en) * | 2016-07-04 | 2019-11-04 | 동우 화인켐 주식회사 | A resist stripper composition, method for manufacturing a display device and display device |
| CN108129463B (en) * | 2018-01-24 | 2021-03-16 | 广东工业大学 | Dioxolane imidazoline compound, preparation method thereof and corrosion inhibitor |
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| CN1699530A (en) * | 2004-03-19 | 2005-11-23 | 气体产品与化学公司 | Process solutions containing surfactants |
| CN101964161A (en) * | 2009-07-21 | 2011-02-02 | 三星移动显示器株式会社 | Flat panel display device and method of fabricating the same |
| CN102200699A (en) * | 2003-12-16 | 2011-09-28 | 昭和电工株式会社 | Method for removing uncured photosensitive composition film or uncured photosensitive composition |
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| WO2007010881A1 (en) * | 2005-07-19 | 2007-01-25 | Showa Denko K.K. | Removing solution for photosensitive composition |
| US20080096785A1 (en) * | 2006-10-19 | 2008-04-24 | Air Products And Chemicals, Inc. | Stripper Containing an Acetal or Ketal for Removing Post-Etched Photo-Resist, Etch Polymer and Residue |
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| CN102200699A (en) * | 2003-12-16 | 2011-09-28 | 昭和电工株式会社 | Method for removing uncured photosensitive composition film or uncured photosensitive composition |
| CN1699530A (en) * | 2004-03-19 | 2005-11-23 | 气体产品与化学公司 | Process solutions containing surfactants |
| CN101964161A (en) * | 2009-07-21 | 2011-02-02 | 三星移动显示器株式会社 | Flat panel display device and method of fabricating the same |
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