JP4405767B2 - Composition for removing photoresist on substrate containing silver and / or silver alloy, method for producing pattern using the same, and display device including the same - Google Patents

Description

  The present invention relates to a photoresist stripping composition for a substrate containing silver and / or a silver alloy, a method for producing a pattern using the same, and a display device including the same.

The organic EL display has a self-luminous property and is expected as a next-generation flat panel display that can achieve lower power consumption, higher brightness, and higher contrast than a liquid crystal display.
As an organic light emitting element, for example, a first electrode, an organic layer including a light emitting layer, and a second electrode are sequentially laminated on a substrate via a TFT (Thin Film Transistor) and a planarizing layer. It has been known. The light generated in the light emitting layer may be extracted from the substrate side, but may be extracted from the second electrode side.

Conventionally, aluminum or aluminum alloy is used as a wiring material in a semiconductor substrate, and in a flat panel, it is also used as a TFT wiring or in recent years as a reflective film of a reflective liquid crystal display (for example, see Patent Document 1). . In addition, materials such as aluminum, aluminum alloys, and chromium have been used as the reflective electrodes of organic EL (see, for example, Patent Document 2).
Usually, a metal reflective film or a reflective electrode is formed by depositing a metal film on a substrate by CVD, sputtering, electrolytic plating, etc., and then applying a photoresist on the metal film, exposing and developing to form a mask. A pattern is formed by wet etching or dry etching with a wet etching solution on the non-mask region of the metal film, and then a photoresist used as a mask is peeled off from the metal film with a photoresist stripping solution. .

Conventional photoresist stripping solutions use phenol and chlorinated hydrocarbon-containing fluids to strip photoresist that has been fixed to the substrate by heating such as post-baking. Compositions containing non as the main component (for example, see Patent Document 3) and mixed solutions of various alkanolamines and 1,3-dimethyl-2-imidazolidinone (for example, see Patent Document 4) have been developed.
Then, since it is necessary to peel off a modified photoresist layer different from the conventional one by adopting dry etching, compositions of various alkanolamines, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide (for example, see Patent Document 5) ), Various alkanolamines, polar organic solvents, and various anticorrosive compositions have been developed.
These compositions can remove the resist-altered layer after dry etching and the photoresist adhered to the substrate, and are used as a photoresist remover for both the dry-etched and wet-etched substrates. be able to.

Examples of the anticorrosive include catechol (for example, see Patent Document 6), weak acids such as phenol and acetic acid (for example, see Patent Document 7), saccharides (for example, see Patent Document 8), catechol, gallic acid ester, and gallic acid. (For example, see Patent Document 9), amino acids (for example, see Patent Document 10), and the like have been reported.
In addition, examples in which hydroxylamine is further added to enhance the stripping ability, and (1) rinsing with isopropyl alcohol is necessary for non-water stripping solutions, (2) amino compounds remain on the metal surface during washing with water. However, there are known disadvantages such as corrosion of the metal, and therefore, examples of water-soluble stripping solutions comprising an organic amino compound, a polar solvent, water, and an anticorrosive agent are known (see, for example, Patent Document 11 and Patent Document 12). ).

  Recently, silver and silver alloys having higher reflectivity than aluminum and aluminum alloys have attracted attention, and a single layer film of silver or a multilayer film including a silver layer has come to be used for a reflection film or a reflection electrode. A multilayer film with a stable oxide film on the silver surface is used to avoid the effects of moisture when the reflective film is exposed to the air and to compensate for the low reflectivity of silver for short-wavelength light. (For example, refer to Patent Document 13 and Patent Document 14) When the silver surface is not exposed to the air, a single layer film of silver is used (for example, refer to Patent Document 13 and Patent Document 15). However, these documents do not disclose any resist stripping liquid used for patterning of a silver film and do not exist in the case of wet etching or dry etching that resists resisting and is difficult to peel off. As the photoresist stripping solution, there is only a photoresist stripping solution that is not corrosive to conventional aluminum and aluminum alloys, and the silver and / or silver alloy is corroded in pattern formation of silver and / or silver alloy. No photoresist stripping solution that can be suitably used without any development has been developed so far.

  As described above, there is a need for a photoresist stripping composition that is not corrosive to silver and / or a silver alloy and has high stripping properties to the photoresist and the altered photoresist layer.

JP 2003-57674 A JP 2002-216976 A JP 63-50838 A JP-A-63-208043 JP-A-4-350660 Japanese Patent Laid-Open No. 5-281653 JP-A-6-202345 JP-A-8-202051 JP 9-296200 A JP-A-7-295240 JP-A-4-289866 JP-A-6-266119 JP 2000-8184 A JP 2002-139609 A JP 2003-228071 A

  Accordingly, an object of the present invention is to provide a photoresist stripping solution composition which can be applied to a substrate containing silver and / or a silver alloy, which solves the above problems.

Amino compounds used in conventional photoresist stripping solutions are classified into amino compounds having a hydroxyl group (alkanolamino) and amino compounds having no hydroxyl group.
Examples of amino compounds having a hydroxyl group include monoethanolamine, monoisopropanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, 2- (2-aminoethylamino) ethanol, 2- (2 -Aminoethylamino) -2-propanol, 2- (2-aminoethoxy) ethanol, diethanolamine, diisopropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, Examples include N-methyldiethanolamine, N- (3-aminopropyl) -N- (2-hydroxyethyl) -2-aminoethanol, trietalamine, and triisopropanolamine.

Examples of amino compounds having no hydroxyl group include diethylenetriamine, triethylenetetramine, dipropylenetriamine, and morpholine derivatives.
However, in reconsidering a photoresist stripping composition that can be suitably applied to a substrate containing silver and / or a silver alloy, conventional amino compounds, such as monoethanolamine, used in aluminum and aluminum alloys are reconsidered. The use of the photoresist stripping solution as the main component has high stripping properties, but it has been found that if it is used as it is, it will corrode silver and silver alloys.

Furthermore, diethanolamine, trietalamine, N, N-dimethylethanolamine, etc., which further has a substituent on the amino group of monoethanolamine, have little corrosion on silver and silver alloys, as will be described later. It became clear that it was difficult to peel off the property, especially the altered photoresist layer.
Therefore, the present inventors diligently and intensively studied to solve the above problems comprehensively. When the carbon chain length of the alkylene chain of the organic amino compound is too long, the peelability is lowered. In addition, it increases the corrosiveness to silver alloys and introduces heteroatoms between the alkylene chains, preventing deterioration of peelability even if the carbon chain length of the alkylene group has a certain length. As a result of further research, we found that certain organic amino compounds and monoethanolamine can be used as photoresist stripping solutions by adding certain anticorrosives. The present invention has been completed.

式中、ＲはＨ、炭素数１〜５のアルキル基、炭素数１〜５のヒドロキシアルキル基または炭素数１〜５のアミノアルキル基である、
で表される化合物、
−ピロカテコール、
−ハイドロキノン、
−ピロガロール、
−没食子酸、及び
−没食子酸エステル
からなる群から選択される１種または２種以上と、１種または２種以上の極性有機溶剤とを含有する、前記フォトレジスト剥離液組成物に関する。
さらに、本発明は、非水系である、前記フォトレジスト剥離液組成物に関する。 That is, the present invention is a photoresist stripping composition for a substrate containing silver and / or a silver alloy,
-Formula (I)
_{NH 2 -A-Y-B-} Z
In the formula, A and B are each independently a linear or branched alkylene group having 1 to 5 carbon atoms, Y is either NH or O, and Z is NH ₂ , OH, NH—D—NH ₂ (wherein D is a linear or branched alkylene group having 1 to 5 carbon atoms),
A compound represented by
-Formula (II)
_{NH 2 -A-N (-B-} OH) 2
In the formula, A and B are the same as in formula (I).
A compound represented by
-Formula (III)

In the formula, R is H, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aminoalkyl group having 1 to 5 carbon atoms,
A compound represented by
-Pyrocatechol,
-Hydroquinone,
-Pyrogallol,
The present invention relates to the photoresist stripping composition comprising one or more selected from the group consisting of gallic acid and gallic acid ester and one or more polar organic solvents.
Furthermore, the present invention relates to the photoresist stripping composition that is non-aqueous.

  In the present invention, the compound represented by formula (I), formula (II) or formula (III) is diethylenetriamine, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) -2. The photo, which is -propanol, N- (3-aminopropyl) -N- (2-hydroxyethyl) -2-aminoethanol, 2- (2-aminoethoxy) ethanol, dipropylenetriamine, triethylenetetramine, morpholine. The present invention relates to a resist stripping composition.

Furthermore, this invention relates to the said photoresist stripping liquid composition whose total content of the compound represented by Formula (I), Formula (II) or Formula (III) is 20 mass% or more and 50 mass% or less. .
The present invention also includes a compound represented by formula (I), formula (II) or formula (III), wherein the polar organic solvent is 1,3-dimethyl-2-imidazolidinone, diethylene glycol monobutyl ether, propylene The present invention relates to the photoresist stripping composition, which is glycol or dimethyl sulfoxide.
The present invention also relates to the photoresist stripping solution further containing an anticorrosive agent.

The present invention also relates to the photoresist stripping composition comprising monoethanolamine and one or more selected from the group consisting of pyrocatechol, hydroquinone, pyrogallol, gallic acid and gallic acid ester. .
Furthermore, the present invention is a photoresist stripping composition comprising monoethanolamine and one or more selected from the group consisting of pyrocatechol, hydroquinone, pyrogallol, gallic acid and gallic acid ester. In addition, the present invention relates to the photoresist stripping composition, wherein the polar organic solvent is N-methyl-2-pyrrolidinone and / or 1,3-dimethyl-2-imidazolidinone.

The present invention also includes a step of forming a metal reflective film or reflective electrode made of silver and / or a silver alloy in a predetermined region on a substrate, and a mask is formed on the metal reflective film or reflective electrode using a photoresist. Etching the metal reflective film or reflective electrode in a non-mask region, and peeling the photoresist from the metal reflective film or reflective electrode using the photoresist stripping solution composition. Alternatively, the present invention relates to a silver alloy pattern forming method.
Furthermore, this invention relates to the pattern formation method of the said silver and / or silver alloy whose etching process is dry etching.

The present invention is also a display device comprising a plurality of display elements on a substrate, wherein the display elements are formed on a layer containing silver and / or a silver alloy on the substrate, and then a photoresist is formed on the laminated film. A silver and / or silver alloy formed by forming a mask using the mask, etching the laminated film using the mask, and peeling the photoresist on which the mask is formed with the photoresist stripping solution The present invention relates to a display device including a reflective film or a reflective electrode.
Furthermore, in the present invention, an organic layer including a light emitting layer and an electrode are sequentially laminated on a reflective film or a reflective electrode made of silver and / or a silver alloy, and the display element transmits light generated in the light emitting layer to the electrode side It is related with the said display apparatus which is an organic light emitting element taken out from.
Further, according to the present invention, a display element includes a substrate, a pixel electrode, a driving element and a wiring electrically connected to the pixel electrode, and a reflective film or a reflective electrode made of silver and / or a silver alloy. The present invention relates to the display device, which is a liquid crystal display element provided between the substrate and the driving element and wiring.

The photoresist stripping composition of the present invention employs a configuration using a specific organic amino compound represented by formula (I), formula (II), or formula (III) or a specific anticorrosive agent. The photoresist after etching of the substrate containing silver and / or silver alloy can be stripped without corroding the silver and silver alloy.
The mechanism of the organic amino compound used in the present invention is not clear, but has a plurality of alkylene groups having a specific number of carbon atoms in the structure of the compound, and when the carbon chain length of the alkylene group is too long, The peelability decreases, and if it is short, the corrosivity increases with respect to silver and silver alloys. Therefore, by applying a specific length of the constitution of the present invention, it is applied to a substrate containing silver and / or silver alloy. Can do.
In addition, even a photoresist deteriorated layer after dry etching can be peeled off satisfactorily without corroding silver and / or a silver alloy, enabling dry etching which has been considered difficult in the past.

式中、ＲはＨ、炭素数１〜５のアルキル基、炭素数１〜５のヒドロキシアルキル基または炭素数１〜５のアミノアルキル基である、
で表される化合物、ピロカテコール、ハイドロキノン、ピロガロール、没食子酸及び没食子酸エステルとからなる群から選択される１種または２種以上と、１種または２種以上の極性有機溶剤とを含有するフォトレジスト剥離液組成物である。
本発明に用いられるフォトレジスト剥離液組成物は、水を含有しない、非水系であることが好ましい。水を含有する場合、剥離液に含有される成分が水と反応してアルカリ性を示し、銀側面を腐食したり粒界に入り込み画素内の腐食を進行させ、欠陥が増加することがあるからである。 Hereinafter, embodiments of the present invention will be described in detail.
The photoresist stripping composition of the present invention has the formula (I)
_{NH 2 -A-Y-B-} Z
In the formula, A and B are each independently a linear or branched alkylene group having 1 to 5 carbon atoms, Y is either NH or O, and Z is NH ₂ , OH, NH—D—NH ₂ (wherein D is a linear or branched alkylene group having 1 to 5 carbon atoms),
A compound represented by formula (II):
_{NH 2 -A-N (-B-} OH) 2
In the formula, A and B are the same as those in formula (I).
A compound represented by formula (III)

In the formula, R is H, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aminoalkyl group having 1 to 5 carbon atoms,
A photo containing one or more selected from the group consisting of a compound represented by the formula: pyrocatechol, hydroquinone, pyrogallol, gallic acid and gallic acid ester, and one or more polar organic solvents It is a resist stripping solution composition.
The photoresist stripping composition used in the present invention preferably contains no water and is non-aqueous. When water is contained, the component contained in the stripper reacts with water to show alkalinity, corroding the silver side surface or entering the grain boundary, causing the corrosion in the pixel to progress, and increasing defects. is there.

式中、ＲはＨ、炭素数１〜５のアルキル基、炭素数１〜５のヒドロキシアルキル基または炭素数１〜５のアミノアルキル基である、
で表される化合物とからなる群から選択される有機アミノ化合物は、銀及び／又は銀合金を含む基板のフォトレジスト剥離液組成物の成分として使用できることが判明した。 That is, the formula (I)
_{NH 2 -A-Y-B-} Z
Wherein, A, B is a linear or branched, an alkylene group having 1 to 5 carbon atoms, Y is either NH or _{O, Z} is NH 2, OH, NH-D- NH ₂ (wherein D is a linear or branched alkylene group having 1 to 5 carbon atoms),
A compound represented by formula (II):
_{NH 2 -A-N (-B-} OH) 2
Wherein, A, and B is same as the formula (I),
And a compound of formula (III)

In the formula, R is H, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aminoalkyl group having 1 to 5 carbon atoms,
It was found that an organic amino compound selected from the group consisting of the compounds represented by the above can be used as a component of a photoresist stripping composition for a substrate containing silver and / or a silver alloy.

Here, since A and B in the above formula ( I ) and formula ( II ) are deteriorated in peelability when the carbon chain length of the alkylene chain is too long, and corroded with respect to silver and the silver alloy when short, A linear or branched alkylene group having 1 to 5 carbon atoms, and considering the photoresist peelability and the corrosiveness to silver, the total number of carbon atoms of A and B is preferably 2 to 10, More preferably, it is 2-6.

Among these compounds, diethylenetriamine, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) -2-propanol, N- (3-aminopropyl) -N- (2-hydroxyethyl) -2-Aminoethanol, 2- (2-aminoethoxy) ethanol, dipropylenetriamine, triethylenetetramine, and morpholine are preferred.
Further, the content of the organic amino compound is preferably 20% by mass or more and 50% by mass or less in consideration of the peeling performance of the photoresist and the altered photoresist layer and the corrosiveness to silver and the silver alloy.

  The polar organic solvent mixed with the organic amino compound represented by the formula (I), formula (II), or formula (III) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol. Monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, di Propylene glycol monobutyl ether, diethylene glycol dimethyl ether, dipropylene Ether solvents such as glycol dimethyl ether, formamide, monomethylformamide, dimethylformamide, monoethylformamide, diethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide and other amide solvents, N-methyl-2-pyrrolidinone Pyrrolidinone solvents such as N-ethyl-2-pyrrolidinone, alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol and propylene glycol, sulfoxide solvents such as dimethyl sulfoxide, 1,3-dimethyl- 2-Imidazolidinone, 1,3-Diethyl-2-imidazolidinone, 1,3-Diisopropyl-2-imidazolidinone Imidazolidinone solvents, .gamma.-butyrolactone, and a lactone-based solvents such as .gamma.-valerolactone.

  Of these, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, N-methyl-2-pyrrolidinone , N-ethyl-2-pyrrolidinone, diethylene glycol monobutyl ether, propylene glycol, and dimethyl sulfoxide are preferable, and from the viewpoint of the removal property of the altered photoresist layer, 1,3-dimethyl-2-imidazolidinone, diethylene glycol mono Butyl ether, propylene glycol, dimethyl sulfoxide.

  In addition, the present composition containing the organic amino compound represented by the formula (I), the formula (II), and the formula (III) and a polar organic solvent is an organic acid such as aminoacetic acid or acetic acid, phloroglucinol, resorcinol, Phenol, benzotriazole, pyrocatechol, hydroquinone, gallic acid, gallic acid ester, pyrogallol and the like can be further added as an anticorrosive.

Moreover, this invention consists of 1 type (s) or 2 or more types selected from the group which consists of monoethanolamine, 1 type, or 2 or more types of polar organic solvents, and pyrocatechol, hydroquinone, pyrogallol, gallic acid, gallic acid ester. A photoresist stripping composition containing an anticorrosive.
However, it is similar to pyrocatechol, hydroquinone, pyrogallol, gallic acid, gallic acid ester, and phloroglucinol (1,3,5-trihydroxybenzene) used as an anticorrosive for conventional photoresist stripping liquid compositions. ), Resorcinol (1,3-dihydroxybenzene), phenol, acetic acid and aminoacetic acid are not improved in corrosiveness to silver and silver alloys even when added together with monoethanolamine.

  The polar organic solvent mixed with monoethanolamine is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Ethers such as propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether Solvent, formamide, monomethylformamide, dimethylformamide, monoethylformamide, diethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide and other amide solvents, N-methyl-2-pyrrolidinone, N-ethyl-2 -Pyrrolidinone solvents such as pyrrolidinone, alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, sulfoxide solvents such as dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, Imidazolidinone solvents such as 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, and γ-butyrolac And lactone solvents such as γ-valerolactone. N-methyl-2-pyrrolidinone and / or 1,3-dimethyl-2-imidazolidinone are preferred.

A display device manufactured using this photoresist stripping solution will be described below.
[First Embodiment]
FIG. 1 shows a schematic cross-sectional view of this display device.
On the glass substrate 11, the TFT 12, the interlayer insulating film 12A, and the wiring 12B are formed.
Next, the planarizing layer 13 is formed on the entire surface of the substrate 11 by, for example, spin coating, and the planarizing layer 13 is patterned into a predetermined shape by exposure and development, and the connection hole 13A is formed. After that, in order to imidize polyimide, it is baked at a temperature of 320 ° C. in a clean baking furnace.
Subsequently, silver or a silver alloy is laminated to a thickness of, for example, 100 nm as the electrode layer 14 containing Ag on the planarizing layer 13 by, for example, sputtering.
After the electrode layer 14 containing Ag is formed, a resist mask is prepared using, for example, a lithography technique, and the electrode layer 14 containing Ag is etched using the resist mask. This etching can be performed by wet etching or dry etching.
Next, the resist is removed with a photoresist stripping solution.

Next, an insulating film 15 is formed over the entire surface of the substrate 11 by, for example, a CVD (Chemical Vapor Deposition) method, and a portion corresponding to the light emitting region is selected from the insulating film 15 by using, for example, a lithography technique. Then, the openings 15A are formed.
Next, the auxiliary electrode 17A is formed on the entire surface of the substrate 11 on the insulating film 15, and selectively etched using, for example, a lithography technique and patterned into a predetermined shape.
Subsequently, the organic layer 16 is formed, for example, by vapor deposition. At that time, a metal vapor deposition mask having an opening is used so as to form a film on the opening of the insulating film 15.
After the organic layer 16 is formed, a common electrode 17 formed by, for example, vapor deposition is formed over the entire surface of the substrate. As a result, the common electrode 17 is electrically connected to the already formed auxiliary electrode 17A and a trunk-like auxiliary electrode which is a bus bar (not shown).

Thereafter, an adhesive layer 30 made of a thermosetting resin is applied and formed on the sealing substrate 21 on the side of the substrate 11 where the organic layer 16 is formed, and the display device is completed.
In this display device, for example, when a predetermined voltage is applied between the electrode layer 14 containing Ag and the common electrode 17, light emission occurs in the organic layer 16.
By using the photoresist stripping solution according to the present invention, the resist can be stripped without corrosion of Ag. For this reason, pixel defects caused by Ag corrosion can be reduced to 1/10 compared with conventional stripping solutions, and the reliability of the display element is improved.

[Second Embodiment]
FIG. 2 shows a cross-sectional structure of a display device according to the second embodiment of the present invention.
This display device is used as a transmissive / reflective (semi-transmissive) liquid crystal display, in which a drive panel 60 and a counter panel 70 are arranged to face each other, and a liquid crystal 80 is provided therebetween. In the drive panel 60, pixel electrodes 62 are provided in a matrix on a substrate 61 made of glass, for example. On the substrate 61, an active driving circuit including a TFT 63 as a driving element electrically connected to the pixel electrode 62, a wiring 63A, and the like is formed.
An alignment film 64 is provided on the entire surface of the substrate 61 facing the liquid crystal 80, and a polarizing plate 65 is provided on the opposite side.

  The pixel has a pixel electrode 62 and an electrode layer 14 containing Ag. The pixel electrode 62 is made of, for example, ITO, and the electrode layer 14 containing Ag is made of a layer containing silver or a silver alloy. The electrode layer 14 containing Ag is formed so as to overlap with a partial region of the pixel electrode 62. A region where the electrode layer 14 containing Ag is formed becomes a reflective display region, and a region where the electrode layer 14 containing Ag of the pixel electrode 62 is not overlapped becomes a transmissive display region.

A gate electrode (not shown) of the TFT 63 is connected to a scanning circuit (not shown), a source (not shown) is connected to a wiring 63A as a signal line, and a drain (not shown) is connected to the pixel electrode 62. ing. The material of the wiring 63A is the same as that of the wiring 13B of the first embodiment. Further, the configuration of the TFT 63 is not particularly limited as in the TFT 12 of the first embodiment. The TFT 63 and the wiring 63A are covered with a protective film 63B made of, for example, silicon oxide (SiO ₂ ) or silicon nitride (SiN).
As the alignment film 64, for example, a film obtained by rubbing (orienting) an organic compound such as polyimide is used. In this case, the pretilt angle is controlled by changing the rubbing condition.
The polarizing plate 65 is an optical element that changes light from a backlight (not shown) into linearly polarized light in a certain direction, and includes, for example, a polyvinyl alcohol (PVA) film.

The counter panel 70 is located on the pixel electrode 62 side of the drive panel 60 and has a counter substrate 71 made of glass or the like.
On the counter substrate 71, for example, a transparent electrode 72 and a color filter 73 are sequentially stacked from the counter substrate 71 side so as to face the pixel electrode 62.
The counter substrate 71 is provided with a light absorption film 74 as a black matrix along the boundary of the color filter 73. An alignment film 75 is provided on the entire surface of the counter substrate 71 facing the liquid crystal 80, and a polarizing plate 76 is provided on the opposite side.

The transparent electrode 72 is made of, for example, ITO.
The light absorbing film 74 absorbs external light incident on the counter substrate 71 or reflected light of the external light reflected by the wiring 64 and improves the contrast. For example, the optical density mixed with a black colorant is increased. It is composed of one or more black resin films or a thin film filter using interference of thin films. The thin film filter is formed by, for example, laminating one or more thin films made of metal, metal nitride, or metal oxide, and attenuating light using interference of the thin film.

Specific examples of the thin film filter include those in which chromium and chromium oxide (III) (Cr ₂ O ₃ ) are alternately laminated. The alignment film 75 and the polarizing plate 76 are configured similarly to the alignment film 64 and the polarizing plate 65 of the drive panel 60.
The liquid crystal 80 changes the transmittance by changing the alignment state by applying a voltage. If the direction in which the liquid crystal molecules incline is not uniform during driving, unevenness in brightness and darkness will occur. To avoid this, a slight pretilt angle is given to the liquid crystal 80 in a certain direction in advance.

This display device can be manufactured, for example, as follows.
First, the electrode layer 14 including the pixel electrode 62 and Ag is formed on the substrate 61 by, for example, a sputtering method. Thereafter, a resist pattern is formed using a photolithography process.
Thereafter, the electrode layer 14 containing Ag is etched using a pattern formed of a photoresist as a mask. Etching can be performed by wet etching using a chemical solution or dry etching. Thereafter, the resist is removed with the photoresist stripping solution described in the first embodiment.
Further, in order to form a pattern of the pixel electrode 62, a resist pattern is similarly formed, and after the etching, the resist is removed with the photoresist stripping solution.

Subsequently, a TFT 63 and a wiring 63A are formed and covered with a protective film 63B. After that, an alignment film 64 is formed on the entire surface of the substrate 61 and a rubbing process is performed. Thereby, the drive panel 60 is formed.
In addition, a transparent electrode 72, a light absorption film 74, and a color filter 73 are formed on the surface of the counter substrate 71. Next, an alignment film 75 is formed on the entire surface of the counter substrate 71, and a rubbing process is performed. Thereby, the opposing panel 70 is formed.

Next, a sealing material (not shown) made of, for example, an epoxy resin is provided around the drive panel 60 or the counter panel 70, and spherical or columnar spacers (not shown) are provided. Subsequently, the driving panel 60 and the counter panel 70 are aligned so that the pixel electrode 62 and the transparent electrode 72 are opposed to each other, and are bonded together by curing a sealing material, and the liquid crystal 80 is injected into the inside and sealed. After that, the polarizing plate 65 is attached to the drive panel 60 and the polarizing plate 76 is attached to the counter panel 70. Thus, the display device shown in FIG. 2 is completed.
By using the photoresist stripping solution of the present invention, the surface of the electrode layer 14 containing Ag as a reflective film is not corroded, and the reliability of the display device due to a decrease in reflectivity due to corrosion or the like is improved.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
1. Non-aqueous photoresist stripping solution containing compound represented by formula (I), formula (II), formula (III) and polar organic solvent (1) Photoresist and photoresist altered layer peelability evaluation Glass substrate A silver alloy film was formed thereon, dry etching was performed using a photoresist coated, exposed, and developed on the silver alloy as a mask to form a pattern, thereby obtaining a photoresist and an altered photoresist layer evaluation substrate. Subsequently, the substrate was immersed in a photoresist stripping solution at 70 ° C. for 10 minutes, rinsed with running water with ultrapure water, dried by nitrogen blowing, and then stripped of photoresist and photoresist with an optical microscope and an electron microscope. Evaluation was performed. The results are shown in Table 1.

(2) Corrosion Evaluation for Silver and Silver Alloy A silver alloy film was formed on a glass substrate to obtain a corrosion evaluation substrate for silver alloy. Subsequently, the substrate was immersed in a photoresist stripping solution at 70 ° C. for 10 minutes, rinsed with running water with ultrapure water, dried with nitrogen blow, and then evaluated for corrosiveness to the silver alloy with an optical microscope and an electron microscope. went. The results are shown in Table 1.

2. A nonaqueous photoresist containing monoethanolamine, a polar organic solvent, and one or more anticorrosive agents selected from the group consisting of pyrocatechol, hydroquinone, pyrogallol, gallic acid, and gallic acid ester Stripping liquid composition The composition was subjected to an experimental evaluation in the same manner as 1 with respect to the photoresist removability and the corrosiveness to the silver alloy, and the results are shown in Table 2.

  By using the photoresist stripping solution of the present invention, the photoresist after etching silver and the silver alloy and the altered photoresist layer after dry etching are stripped without corroding the silver and the silver alloy. Therefore, it becomes possible to manufacture an organic EL display using silver and a silver alloy as a metal reflection film.

1 is a schematic cross-sectional view of a first embodiment of a display device of the present invention. It is the one section schematic of the 2nd embodiment of the display of the present invention.

Explanation of symbols

11 ... Glass substrate 12 ... TFT
12A ... Interlayer insulating film 12B ... Wiring 13 ... Flattened layer 13A ... Connection hole 14 ... Electrode layer 15 ... Insulating film 15A ...・ Opening 16 ... Organic layer 17 ... Common electrode
17A ... Auxiliary electrode 21 ... Sealing substrate 30 ... Adhesive layer 60 ... Drive panel 61 ... Substrate 62 ... Pixel electrode 63 ... .... TFT
63A ... Wiring 63B ... Protective film 64 ... Alignment film 65 ... Polarizing plate 70 ... Counter panel 71 ... Counter substrate 72 ...・ Transparent electrode 73 ... Color filter 74 ... Light absorption film 75 ... Alignment film 76 ... Polarizing plate 80 ... Liquid crystal

Claims (11)

A photoresist stripping liquid composition for use in a substrate containing silver and / or a silver alloy, for preventing corrosion of silver and / or a silver alloy and stripping the photoresist and the altered photoresist layer,
-Formula (I)
_{NH 2 -A-Y-B-} Z
In the formula, A and B are each independently a linear or branched alkylene group having 1 to 5 carbon atoms, Y is either NH or O, and Z is NH ₂ , OH, NH—D—NH ₂ (wherein D is a linear or branched alkylene group having 1 to 5 carbon atoms),
A compound represented by
-Formula (II)
_{NH 2 -A-N (-B-} OH) 2
In the formula, A and B are the same as in formula (I).
A compound represented by, and - formula (III)

In the formula, R is H, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aminoalkyl group having 1 to 5 carbon atoms,
A compound represented by
One or more selected from the group consisting of:
Ether solvents, amide solvents, pyrrolidinone solvents, alcohol solvents, sulfoxide solvents, consists of a two or more polar organic solvents that will be selected from the group consisting of imidazolidinone solvents and lactone solvent, a non-aqueous The photoresist stripping composition.   Compounds represented by formula (I), formula (II) or formula (III) are diethylenetriamine, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) -2-propanol, N- One selected from the group consisting of (3-aminopropyl) -N- (2-hydroxyethyl) -2-aminoethanol, 2- (2-aminoethoxy) ethanol, dipropylenetriamine, triethylenetetramine and morpholine The photoresist stripping composition according to claim 1, wherein the composition is two or more.   The photoresist stripping composition according to claim 1 or 2, wherein the total content of the compounds represented by formula (I), formula (II) or formula (III) is 20% by mass or more and 50% by mass or less. . A compound represented by the formula (I), the formula (II) or the formula (III), wherein the polar organic solvent is 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidinone, diethylene glycol monobutyl ether it is 2 or more that will be selected from the group consisting of propylene glycol, and dimethyl sulfoxide, the photoresist stripping liquid composition according to any one of claims 1 to 3. A photoresist stripping liquid composition for use in a substrate containing silver and / or a silver alloy, for preventing corrosion of silver and / or a silver alloy and stripping a photoresist and a modified photoresist layer, and comprising monoethanolamine If, ether solvents, amide solvents, pyrrolidinone solvent, and alcohol solvents, sulfoxide solvents, two or more polar organic solvents that will be selected from the group consisting of imidazolidinone solvents and lactone solvent, pyrocatechol, hydroquinone, pyrogallol, made of one or more anticorrosive agent selected from the group consisting of gallic acid and gallic acid esters, non-aqueous, the photoresist stripping liquid composition. Polar organic solvent, N- methyl-2-pyrrolidinone及beauty 1, 3-dimethyl-2-imidazolidinone, a photoresist stripping liquid composition according to claim 5. Forming a metal reflective film or reflective electrode made of silver and / or a silver alloy in a predetermined region on the substrate; forming a mask on the metal reflective film or reflective electrode using a photoresist; Etching a metal reflective film or a reflective electrode, and peeling the photoresist from the metal reflective film or the reflective electrode using the photoresist stripping liquid composition according to any one of claims 1 to 6. , Silver and / or silver alloy pattern forming method. The method for forming a silver and / or silver alloy pattern according to claim 7 , wherein the etching step is dry etching. A method of manufacturing a display device including a plurality of display elements on a substrate, wherein the display element is formed by forming a layer containing silver and / or a silver alloy on the substrate and then using a photoresist on the laminated film. formed by forming a mask, etching the film described above laminated using the mask, the photoresist forming the mask is peeled off with the photoresist stripping liquid composition according to any one of claims 1 to 6 The manufacturing method of the display apparatus provided with the reflective film or reflective electrode which was made from silver and / or a silver alloy. The display element is an organic light emitting element in which an organic layer and an electrode including a light emitting layer are sequentially laminated on a reflective film or a reflective electrode made of silver and / or a silver alloy, and light generated in the light emitting layer is extracted from the electrode side. A method for manufacturing a display device according to claim 9 . The display element is provided with a pixel electrode, a drive element and a wiring electrically connected to the pixel electrode, and a reflective film or a reflective electrode made of silver and / or a silver alloy is provided on the substrate and the drive. The method for manufacturing a display device according to claim 9 , wherein the display device is a liquid crystal display element provided between the element and the wiring.

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