KR20100122739A - Method of fabricating thin film transistor substrate and photoresist composition used therein - Google Patents

Abstract

PURPOSE: A manufacturing method of a thin film transistor substrate is provided to reduce the fault of a pattern when forming a micro circuit pattern, and to decrease the manufacturing time with the short photosensitive speed. CONSTITUTION: A manufacturing method of a thin film transistor substrate comprises the following steps: forming a conductive layer with a conductive material on a substrate; forming an etching pattern formed with a photoresist composition on the conductive layer; and using the etching pattern as an etching mask to etch the conductive layer, for forming a conductive layer pattern. The photoresist composition contains a first novolak resin, a binder resin containing a second novolak resin, a photo-sensitizer containing a diazide based compound, and a solvent.

Description

Method of fabricating thin film transistor substrate and photoresist composition used therein

The present invention relates to a method for manufacturing a thin film transistor array panel and a photoresist composition used therein, and more particularly, to a method for manufacturing a thin film transistor array panel in which defects in fine patterns are reduced and a process time is shortened, and a photoresist composition used therein. It is about.

In order to form a fine circuit pattern such as a display device circuit or a semiconductor integrated circuit, first, a photoresist composition is uniformly coated or coated on an insulating film or a conductive metal film on a substrate. The coated photoresist composition is then exposed and developed in the presence of a mask of the desired shape to form a pattern of the desired shape. Thereafter, the metal film or the insulating film is etched using a mask, and the remaining photoresist film is removed to form a microcircuit on the substrate.

Meanwhile, as the high performance of electronic devices is required, the degree of integration of devices is increased, and in order to integrate a plurality of devices on a limited substrate, it is necessary to implement a fine circuit pattern. Accordingly, studies have been made to improve the resolution and the like of the photoresist composition used in forming the microcircuit pattern.

In order to form the microcircuit pattern, the photoresist composition should have an improved photosensitivity, residual film ratio, development contrast, resolution, solubility of the polymer resin, adhesion to the substrate, and circuit uniformity (CD uniformity).

As a result, when the microcircuit pattern is formed, defects in the pattern can be reduced, and process time can be shortened.

An object of the present invention is to provide a method for manufacturing a thin film transistor array panel in which defects in fine patterns are reduced and process time is shortened.

Another object of the present invention is to provide a photoresist composition having improved photosensitivity, residual film ratio, development contrast, resolution, and the like.

Problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

According to an aspect of the present invention, there is provided a method of manufacturing a thin film transistor array panel, the method including forming a conductive film made of a conductive material on a substrate, and an etching pattern made of a photoresist composition on the conductive film. Forming a conductive layer pattern by etching the conductive layer using the etching pattern as an etching mask, wherein the photoresist composition is formed of a first novolac resin, The binder resin containing the displayed 2nd novolak resin, the photosensitive agent containing a diazide type compound, and a solvent can be included.

[Formula 1]

Here, R1 to R4 are alkyl groups.

[Formula 2]

Here, R1 to R5 are alkyl groups.

The photoresist composition according to an embodiment of the present invention for achieving another object to be solved is a binder resin containing a first novolak resin and a second novolak resin represented by the following formula (1) or (2), It may include a photosensitive agent and a solvent including a diazide compound.

[Formula 1]

Here, R1 to R4 are alkyl groups.

[Formula 2]

Here, R1 to R5 are alkyl groups.

Specific details of other embodiments are included in the detailed description and the drawings.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only the embodiments make the disclosure of the present invention complete, and the general knowledge in the technical field to which the present invention belongs. It is provided to fully convey the scope of the invention to those skilled in the art, and the present invention is defined only by the scope of the claims. In the drawings, the sizes and relative sizes of layers and regions may be exaggerated for clarity.

When elements or layers are referred to as "on" or "on" of another element or layer, intervening other elements or layers as well as intervening another layer or element in between. It includes everything. On the other hand, when a device is referred to as "directly on" or "directly on", it means that no device or layer is intervened in the middle. Like reference numerals refer to like elements throughout. “And / or” includes each and all combinations of one or more of the items mentioned.

The terms spatially relative, "below", "beneath", "lower", "above", "upper" May be used to readily describe a device or a relationship of components to other devices or components. Spatially relative terms should be understood to include, in addition to the orientation shown in the drawings, terms that include different orientations of the device during use or operation.

Embodiments described herein will be described with reference to plan and cross-sectional views, which are ideal schematic diagrams of the invention. Accordingly, shapes of the exemplary views may be modified by manufacturing techniques and / or tolerances. Accordingly, the embodiments of the present invention are not limited to the specific forms shown, but also include variations in forms generated by the manufacturing process. Thus, the regions illustrated in the figures have schematic attributes, and the shape of the regions illustrated in the figures is intended to illustrate a particular form of region of the device, and is not intended to limit the scope of the invention.

Hereinafter, a method of manufacturing a thin film transistor array panel according to a first exemplary embodiment of the present invention will be described in detail with reference to FIGS. 1 to 11.

1 is a layout view of a thin film transistor array panel manufactured by a method according to a first exemplary embodiment of the present invention. FIG. 2 is an enlarged view of a portion A of FIG. 1. 3 is a cross-sectional view taken along the line AA ′ of FIG. 2. 4 through 11 are cross-sectional views illustrating a method of manufacturing a thin film transistor array panel according to a first exemplary embodiment of the present invention.

First, referring to FIGS. 1 to 3, the thin film transistor array panel manufactured according to the first exemplary embodiment of the present invention includes a plurality of pixels arranged in a matrix and a plurality of thin film transistors provided for each pixel. A plurality of gate lines 22 extending along the pixel boundary are arranged in the pixel row direction, and a plurality of data lines 62 extending along the boundary of the pixel are arranged in the pixel column direction. The thin film transistor including the gate electrode 24, the source electrode 65, and the drain electrode 66 is formed in an area where the gate wiring 22 and the data wiring 62 intersect.

The thin film transistor array panel according to the present exemplary embodiment has an AOC (Array On Color filter) structure in which a color filter 131 is formed on an insulating substrate 10 and a thin film transistor array such as a gate wiring is formed on the color filter 131. Although it may have a color filter on array (COA) structure in which the color filter 131 is formed on the transistor array, the structure of the thin film transistor array panel is not limited thereto. Hereinafter, a thin film transistor array panel having an AOC structure will be described as an example.

In the thin film transistor array panel having the AOC structure, a black matrix 121 is formed directly on the insulating substrate 10. Red, green, and blue color filters 131 are sequentially arranged in the pixel region between the black matrices 121. An overcoat layer 136 may be formed on the color filter 131 to planarize these steps.

On the overcoat layer 136, the gate wiring including the gate line 22, the gate electrode 26, and the storage wiring 28, the gate insulating film 30, the semiconductor layer 40, the ohmic contact layers 55 and 56, And a data line including a data line 62, a source electrode 65, and a drain electrode 66. The passivation layer 70 including the contact hole 76 is formed on the data line, and the pixel electrode patterns 84 and 85 are disposed on the passivation layer 70.

The pixel electrode patterns 84 and 85 may be made of a transparent conductive material, for example, ITO or IZO. The pixel electrode patterns 84 and 85 of this embodiment consist of a plurality of fine electrodes 84 and fine slits 85 formed between the fine electrodes 84. Specifically, the pixel electrode patterns 84 and 85 of the present embodiment are, for example, a cross-shaped main skeleton that divides the pixel region into quadrants, a plurality of fine electrodes 84 formed by diagonal lines directed from the main skeleton to the outer side of the pixel region, And a plurality of fine slits 85 disposed between the plurality of fine electrodes 84. The plurality of fine electrodes 84 formed in an oblique direction may be formed in four different directions from the center of the pixel area. Accordingly, when driving power is applied to the liquid crystal display, the liquid crystals (not shown) are aligned in four different directions.

The width of the microelectrode 84 may be the same or different at the center of the pixel electrode patterns 84 and 85, that is, the point where the microelectrode 84 comes into contact with the cruciform main skeleton and the outer portion of the pixel region. When the width of the fine electrode 84 is the same throughout the pixel area, the width w1 of the fine slit 85 may be 2 to 5 μm. Although not shown, the common electrode display panel disposed on the thin film transistor array panel of the present exemplary embodiment may include a non-patterned common electrode. Therefore, when the pixel electrode patterns 84 and 85 adjust the alignment of the liquid crystal (not shown), and the width w1 of the fine slit 85 exceeds 5 μm, the response speed of the liquid crystal may be reduced. In addition, it may be difficult to adjust the width w1 of the fine slit 85 to less than 2 μm under the limitation of the resolution of the exposure machine.

4 and 11, in order to manufacture a thin film transistor array panel, first, an insulating substrate 10 is provided.

The insulating substrate 10 may be made of a glass substrate such as soda lime glass or borosilicate glass or plastic such as polyether sulfone and polycarbonate. In addition, the insulating substrate 10 may be, for example, a flexible substrate made of polyimide or the like.

The insulating substrate 10 may be a size corresponding to a unit thin film transistor array panel used in one liquid crystal display, but may be a large substrate in which a plurality of thin film transistor array panels are manufactured in one insulation substrate 10.

Subsequently, an opaque material such as chromium (Cr) or chromium oxide (CrO _x ) is deposited and patterned on the insulating substrate 10 to form a black matrix 121. Subsequently, for example, a photosensitive resist is applied to the upper surface of the black matrix 121 and the entire surface of the insulating substrate 10 exposed by the black matrix 121, and exposed and developed to apply the red, green, and blue color filters 131. Form. Subsequently, an overcoat layer 136 is formed on the black matrix 121 and the color filter 131.

Subsequently, referring to FIG. 4, after the gate wiring conductive film 20 is stacked on the overcoat layer 136, the gate wiring 22, the gate electrode 26, and the storage wiring 28 are formed by patterning the conductive film 20. A gate wiring is formed. The photoresist pattern 200 used when the gate wiring is formed may use the photoresist composition according to the second embodiment of the present invention. The photoresist composition according to the second embodiment of the present invention will be described later. Here, in order to form the gate wiring including the gate line 22, the gate electrode 26, and the storage wiring 28, the conductive film 20 may be formed using, for example, sputtering. have. Sputtering is performed in a low temperature process of 200 ° C. or less, and then the photoresist patterns 200 are formed on these conductive films 20, and the conductive films 20 are wet-etched or dry-etched using the same as an etching mask. do. In the case of wet etching, an etchant such as phosphoric acid, nitric acid or acetic acid may be used.

Gate wiring includes aluminum-based metals such as aluminum (Al) and aluminum alloys, silver-based metals such as silver (Ag) and silver alloys, copper-based metals such as copper (Cu) and copper alloys, molybdenum (Mo) and molybdenum alloys, etc. It may be made of a molybdenum-based metal, chromium (Cr), titanium (Ti), tantalum (Ta) and the like. In addition, the gate wiring may have a multilayer structure including two conductive layers (not shown) having different physical properties. One of the conductive films is made of a low resistivity metal such as an aluminum-based metal, a silver-based metal, or a copper-based metal so as to reduce the signal delay or voltage drop of the gate wiring. In contrast, the other conductive layer is made of a material having excellent contact properties with other materials, in particular zinc oxide (ZnO), indium tin oxide (ITO) and indium zinc oxide (IZO), such as molybdenum-based metals, chromium, titanium, tantalum and the like. A good example of such a combination is a chromium bottom film and an aluminum top film and an aluminum bottom film and a molybdenum top film. However, the present invention is not limited thereto, and the gate wiring may be formed of various various metals and conductors.

Subsequently, referring to FIG. 5, a gate insulating layer 30 made of silicon nitride (SiNx), silicon oxide, or the like is formed on the insulating substrate 10 and the gate wiring by chemical vapor deposition or sputtering.

Next, referring to FIG. 6, for example, hydrogenated amorphous silicon, polycrystalline silicon, or the like is deposited on the gate insulating layer 30 using chemical vapor deposition or sputtering to form an active layer 40. Subsequently, the ohmic layer 50 is formed on the active layer 40 by laminating n + hydrogenated amorphous silicon doped with silicide or n-type impurities at a high concentration using, for example, chemical vapor deposition or sputtering.

Thereafter, the photoresist pattern 200 is formed on the active layer 40 and the ohmic layer 50, and the active layer 40 and the ohmic layer 50 are patterned using the photoresist pattern 200 as an etching mask. As a result, an active layer pattern (see 44 in FIG. 7) and an ohmic layer pattern (see 54 in FIG. 7) are formed. In the active layer pattern 44, 'active' refers to an active material having electrical characteristics when a driving current is applied, and includes both a semiconductor, a metal oxide, and the like.

The etching used to form the active layer pattern 44 and the ohmic layer pattern 54 may use separate wet etching or dry etching, respectively. In the case of wet etching, an etchant obtained by mixing deionized water with hydrofluoric acid (HF), sulfuric acid, hydrochloric acid, and a combination thereof may be used. In the case of dry etching, a fluorine-based etching gas such as CHF ₃ , CF ₄ or the like can be used. Specifically, an etching gas containing Ar or He may be used as the fluorine-based etching gas.

Next, referring to FIGS. 7 and 8, for example, Ni, Co, Ti, Ag, Cu, Mo, Al, Be, Nb, Au, Fe, Se, Ta, or the like may be used by chemical vapor deposition or sputtering. The data wiring conductive film 60 made of a single film or multiple films is deposited.

Examples of the multilayers include double films such as Ta / Al, Ta / Al, Ni / Al, Co / Al, Mo (Mo alloy) / Cu, or Ti / Al / Ti, Ta / Al / Ta, Ti / Al / TiN, Triple films such as Ta / Al / TaN, Ni / Al / Ni, Co / Al / Co and the like can be exemplified. Subsequently, the photoresist pattern 200 is formed on the data wiring conductive film 60, and the data wiring conductive film 60 is etched using the photoresist pattern 200 as an etching mask, thereby forming the data wiring 62, 65, and the like. 66). Such etching may use wet etching or dry etching. For wet etching, an etchant such as a mixture of phosphoric acid, nitric acid and acetic acid, a mixture of hydrofluoric acid (HF) and deionized water, and the like may be used. At this time, the ohmic layer pattern 54 is etched and separated using the photoresist pattern 200 for etching the conductive film 60 for data wiring. As a result, the ohmic contact layer patterns 55 and 56 are formed to overlap the source electrode 65 and the drain electrode 66.

As a result of the etching, the data lines 62, 65, and 66 are formed in a vertical direction and intersect with the gate line 22 to define a pixel and a branch from the data line 62. The source electrode 65 is branched and extended to the upper portion of the active layer pattern 44, and is separated from the source electrode 65 and faces the source electrode 65 with respect to the channel portion of the gate electrode 26 or the thin film transistor. The drain electrode 66 is formed on the active layer pattern 44.

Referring to FIG. 9, a protective film 70 is formed on the active layer pattern 4 and the data lines 62, 65, 66, and 67. Subsequently, the photoresist pattern 200 is formed on the passivation layer 70 and the contact hole 76 exposing the drain electrode 66 is formed through an etching process using the photoresist pattern 200.

Next, referring to FIG. 10, a conductive film 80 for a pixel electrode made of a transparent conductor or a reflective conductor such as, for example, ITO or IZO is formed. The conductive film 80 for pixel electrodes can be deposited by, for example, sputtering.

Next, referring to FIG. 11, the photoresist composition may be applied onto the conductive film 80 for pixel electrodes using a spray method, a roll coater method, a rotation coating method, or the like.

The applied photoresist composition is then removed at a temperature of 105 ° C. for 1-5 minutes with the solvent contained in the soft bake photoresist composition. As a result, a photoresist film is formed. Thereafter, ultraviolet rays having a wavelength of 365 nm to 435 nm are irradiated to the photoresist film so that the photoresist film has a predetermined pattern shape. Thereafter, the substrate 10 on which the photoresist film is formed is immersed in a developing solution to remove a portion irradiated with ultraviolet rays to form a predetermined photoresist pattern.

At this time, the developer is an aqueous alkali solution, for example inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used.

Subsequently, referring to FIG. 11, the photoresist film may be cleaned with ultrapure water for 30 to 90 seconds to completely remove unnecessary portions and dried to form an etching pattern 200.

The photoresist composition used in the manufacture of the thin film transistor array panel according to the present embodiment includes a photoresist including a first novolak resin, a binder resin containing a second novolak resin represented by Formula 1 or Formula 2, and a diazide compound. Agent and solvent.

 [Formula 1]

Here, R1 to R4 are alkyl groups.

[Formula 2]

Here, R1 to R5 are alkyl groups. The coating thickness d1 of the etching pattern 200 having the composition may be 1 to 2 μm. When the coating thickness d1 of the etching pattern 200 exceeds 2 μm, the exposure amount and the developing time may increase, and thus the pattern shape may have a reverse taper. That is, the pattern profile of the etching pattern 200 may be degraded. This makes it difficult to manufacture fine circuit line widths and the like. In addition, the exposure amount may be increased, and the photosensitive speed may be lowered. As a result, the resolution of the etching pattern 200 may be reduced, and the processing time may be increased. When the coating thickness d1 of the etching pattern 200 is less than 1 μm, a portion to which the photoresist composition is not applied may be formed, which may cause patterning defects. That is, the residual film rate is lowered, and thus the portion of the residual film which is not to be etched by the etching pattern 200 may be etched.

2 and 3, the pixel electrode patterns 84 and 85 are formed by etching the conductive film 80 for the pixel electrode using the etching pattern 200 as an etching mask.

According to the first embodiment, by using the photoresist composition of the second embodiment, which will be described later, in which the photosensitivity, residual film ratio, adhesion to the substrate, and uniformity of the circuit line width are improved, the fine electrode 84 having an excellent pattern is obtained. The pixel electrode patterns 84 and 85 may be formed.

After the pixel electrode patterns 84 and 85 are formed, the etching pattern 200 is removed using a stripper. As a result, the thin film transistor array panel according to the first exemplary embodiment of the present invention is completed.

Hereinafter, a photoresist composition according to a second embodiment of the present invention will be described.

The photoresist composition of the second embodiment includes a binder resin containing a first novolak resin, a second novolak resin represented by Formula 1 or Formula 2, a photosensitizer containing a diazide compound, and a solvent. do.

[Formula 1]

Here, R1 to R4 are alkyl groups.

[Formula 2]

Here, R1 to R5 are alkyl groups.

First, the binder resin included in the photoresist composition according to the second embodiment of the present invention will be described. The binder resin includes a first novolac resin and a second novolac resin represented by Formula 1 or Formula 2.

The first novolac resin is a polymer polymer synthesized by reacting formaldehyde with an aromatic alcohol such as metacresol and para cresol. The monodisperse polystyrene reduced weight average molecular weight of the first novolak resin measured by GPC (Gel Permeation Chromatography) is preferably 2,000 to 10,000. If the average molecular weight is less than 2,000, the viscosity required for the photoresist composition is not satisfied. If the average molecular weight is more than 10,000, the viscosity increases, but it is difficult to uniformly apply the photoresist composition, which may cause a defect of the photoresist pattern.

The content ratio of meta cresol and para cresol constituting the first novolak resin is preferably 30 to 70:70 to 30 parts by weight. When the content of the meta cresol exceeds the above range, the photosensitive rate is increased, and the residual film rate is low. When the content of the para cresol exceeds the above range, the photosensitive rate is slowed.

The second novolak resin is represented by the formula (1) or (2).

[Formula 1]

Here, R1 to R4 are alkyl groups.

[Formula 2]

Here, R1 to R5 are alkyl groups.

The second novolak resin is a polymer polymer synthesized by reacting metacresol, para cresol, xyleneol and the like. Alternatively, the second novolak resin is a polymer polymer synthesized by reacting metacresol, para cresol, trimethylphenyl and the like.

It is preferable that the monodisperse polystyrene reduced weight average molecular weight of the 2nd novolak resin measured by GPC (Gel Permeation Chromatography) is 2,000-10,000. If the average molecular weight exceeds the above range, the viscosity becomes smaller or larger than necessary, which is not good in terms of pattern uniformity and pattern profile.

The second novolak resin may have different properties such as photoresist rate and residual film ratio depending on the content ratio of meta cresol, para cresol and xyleneol or meta cresol, para cresol and trimethylphenyl. Specifically, the content ratio of meta cresol, para cresol and xyleneol or meta cresol, para cresol and trimethylphenyl is preferably 30 to 70:70 to 30: 1 to 40 parts by weight. When the content of the meta cresol exceeds the above range, the photosensitivity is increased, and the residual film rate is low. When the content of the para cresol is above the above range, the photosensitivity is slowed. If it exceeds, residual film rate may fall.

The mixing ratio of the first novolak resin and the second novolak resin contained in the binder resin is 1 to 80: 99 to 20. If the above range is exceeded, the function cannot be exhibited at any part of the photosensitive speed, the pattern profile of the photoresist and the resolution.

The content of the binder resin included in the photoresist composition according to the second embodiment is 5 to 30% by weight. When the content of the binder resin is less than 5% by weight, in the development process performed after exposure, the rate at which the photoresist composition is dissolved by the developing solution may be increased, and the residual film rate of the final thin film pattern may be lowered. When the content of the binder resin exceeds 30% by weight, the rate at which the photoresist composition is dissolved by the developer may be slowed down during the development process that is performed after exposure. As a result, an appropriate sensitivity cannot be obtained with respect to the exposure energy, so that the exposure time can be long, and the thin film pattern formation time as a whole can be long.

Next, a photosensitive agent including a diazide compound included in the photoresist composition according to the second embodiment of the present invention will be described.

Photosensitive agents are 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and 2,3,4,4'-tetrahydroxybenzophenone-1,2- And any compound selected from the group comprising naphthoquinonediazide-5-sulfonate and a compound represented by formula (3). At this time, the mixing ratio is 30 to 70: 70 to 30.

(3)

Wherein R 1 to R 4 are 2-diazo-1-naphthol-5-sulfonyl or hydrogen, and R 5 to R 8 are alkyl or benzyl groups.

If the mixing ratio exceeds the above range, there may be no improved effect in terms of photosensitivity and resolution. The photosensitizer may influence the taper angle of the photoresist pattern or the quality of the pattern profile.

The content of the photosensitive agent included in the photoresist composition according to the second embodiment is 2 to 10% by weight. If the content of the photosensitizer is less than 2% by weight, the photoresist may be prone to light even with a small exposure energy, making it difficult to form a thin film pattern in a desired exposure energy band. When the content of the photosensitizer exceeds 10% by weight, it may be difficult to form a pattern in a desired exposure energy band due to a large amount of energy photosensitive by the light source.

Next, the solvent contained in the photoresist composition according to the second embodiment of the present invention will be described.

The solvent must dissolve the binder resin and the photosensitive agent. The solvent according to the second embodiment is propylene glycol methyl ether acetate (PGMEA), ethyl lactate (EL), ethyl cellulose sole acetate (ECA), 2-methoxyethyl acetate, gamma butyrolactone (GBL), methyl methoxy At least one selected from the group consisting of propionate (MMP), ethylbetaethoxypropionate (EEP), propylene glycol monomethyl ether (PGME), normal propyl acetate (nPAC) and normal butyl acetate (nBA). The content of the solvent is the remaining amount including the binder resin and the photosensitive agent in the entire photoresist composition.

Meanwhile, the photoresist composition according to the second embodiment may further include at least one additive selected from the group consisting of colorants, dyes, anti-scratching agents, plasticizers, adhesion promoters, rate enhancers, and surfactants. Thereby, the performance improvement according to the characteristic of an individual process can be aimed at.

Hereinafter, the photoresist composition according to the second embodiment will be described in more detail with reference to specific experimental examples. However, the technical spirit of the present invention is not limited by the following experimental examples.

(Example 1)

Binder resin mixed 30:70 parts by weight of the first novolak resin having a weight ratio of meta cresol: para cresol to 4: 6 and a second novolak resin having a weight ratio of meta cresol: para cresol to trimethylphenyl at 4: 4: 2. 20 g, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and bis [4-hydroxy-3- (2-hydroxy) as a photosensitizer 50-50 parts by weight of -5-methylbenzyl) -5dimethylphenyl] methane-1,2-naphthoquinonediazide-5-sulfonate was mixed to 4 g and 70 g of propylene glycol methyl ether acetate (PGMEA) as a solvent. Mixed to prepare a photoresist composition.

(Example 2)

Binder resin mixed 30:70 parts by weight of the first novolak resin having a weight ratio of meta cresol: para cresol to 4: 6 and a second novolak resin having a weight ratio of meta cresol: para cresol to trimethylphenyl at 4: 4: 2. 20 g, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and bis [4-hydroxy-3- (2-hydroxy) as a photosensitizer 50-50 parts by weight of -5-methylbenzyl) -5dimethylphenyl] methane-1,2-naphthoquinonediazide-5-sulfonate was mixed to 4 g and 70 g of propylene glycol methyl ether acetate (PGMEA) as a solvent. Mixed to prepare a photoresist composition.

(Bagyo)

20 g of a novolak resin having a weight ratio of meta cresol: para cresol of 4: 6 as a binder resin, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate as a photosensitizer 50 g of 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate was mixed in 50 parts by weight, 4 g, and 60 g of propylene glycol methyl ether acetate (PGMEA) as a solvent. The mixture was uniformly mixed to prepare a photoresist composition.

Experimental Example

The photoresist compositions prepared in Examples 1 and 2 and Comparative Example 1 were spin coated onto the glass substrate at a constant rate. Then, it dried under reduced pressure for 60 second at 0.1 Torr or less. Subsequently, the glass substrate to which the photoresist composition was apply | coated was soft baked at 105 degreeC for 90 second, and the photoresist film of 1.50 micrometer thickness was formed. Subsequently, the uniformity of the photoresist film was measured. Subsequently, ultraviolet rays having a wavelength of 365 nm to 435 nm were exposed to the photoresist film using an exposure machine. Subsequently, the photoresist film was developed at room temperature with an aqueous solution containing tetramethylammonium hydroxide for 70 seconds to form a photoresist pattern.

1) dimming speed and Residual rate

Initial thickness of photoresist film = (thickness of lost photoresist film) + (thickness of remaining photoresist film)

* Residual film ratio = (thickness of remaining photoresist film / thickness of initial photoresist film)

The photosensitive speed was determined by measuring the energy at which the photoresist film completely melted under a certain developing condition according to the exposure energy. Residual film ratio was calculated | required by measuring the thickness of the photoresist film before and behind the image development process of the experiment example mentioned above.

2) Taper angle and pattern profile

As described above, after the photoresist pattern was formed, the taper angle and the pattern profile of the formed photoresist pattern were measured using a scanning electron microscope (SEM).

The measurement results according to the experimental example are shown in Table 1 below.

TABLE 1

division Photospeed mJ / ㎠) Residual rate (%) Taper  Angle (°) Pattern profile Example 1 8 98 30 ◎ Example 2 8 98 40 ◎ Comparative example 14 94 15 X

Note) In Table 1,

(Circle) represents a pattern profile excellent, X represents a pattern profile defect.

Referring to Table 1 and FIGS. 12 to 14, the photoresist compositions according to Examples 1 and 2 have a higher taper angle and a better pattern profile than the photoresist compositions according to Comparative Examples. The higher the taper angle of the photoresist pattern and the better the pattern profile, the larger the margin in the process, so that a pattern having a desired shape can be easily implemented by the photoresist pattern. In addition, the fast photosensitive speed reduces the process time.

Although embodiments of the present invention have been described above with reference to the accompanying drawings, those skilled in the art to which the present invention pertains may implement the present invention in other specific forms without changing the technical spirit or essential features thereof. I can understand that. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

1 is a layout view of a thin film transistor array panel manufactured by a method according to a first exemplary embodiment of the present invention.

FIG. 2 is an enlarged view of a portion A of FIG. 1.

3 is a cross-sectional view taken along the line AA ′ of FIG. 2.

4 through 11 are cross-sectional views illustrating a method of manufacturing a thin film transistor array panel according to a first exemplary embodiment of the present invention.

12 shows a photoresist pattern formed of the photoresist composition according to Example 1. FIG.

FIG. 13 shows a photoresist pattern formed of the photoresist composition according to Example 2. FIG.

14 shows a photoresist pattern formed of a photoresist composition according to a comparative example.

(Explanation of symbols for the main parts of the drawing)

10: insulating substrate 22: gate line

26: gate electrode 28: storage wiring

30: gate insulating film 40: semiconductor layer

55, 56: ohmic contact layer 62: data line

65 source electrode 66 drain electrode

70: shield 76: contact hole

84: fine electrode 85: fine slit

121: black matrix 131: color filter

136: overcoat layer 200: etching pattern

Claims (16)

Forming a conductive film made of a conductive material on the substrate; Forming an etching pattern made of a photoresist composition on the conductive layer; And Etching the conductive layer using the etching pattern as an etching mask to form a conductive layer pattern, The photoresist composition is Binder resin containing a 1st novolak resin, the 2nd novolak resin represented by following formula (1) or (2), the photosensitive agent containing a diazide type compound, and the manufacturing method of the thin film transistor display panel containing a solvent . [Formula 1]

Here, R1 to R4 are alkyl groups. [Formula 2]

Here, R1 to R5 are alkyl groups. The method of claim 1, The coating thickness of the etching pattern is a method of manufacturing a thin film transistor array panel of 1 to 2㎛. The method of claim 1, The conductive film pattern is a pixel electrode pattern made of a transparent conductive material. The method of claim 3, wherein The pixel electrode pattern includes a plurality of fine electrodes and a plurality of fine slits formed between the fine electrodes. The method of claim 4, wherein The width of the fine slit is 2 to 5㎛ manufacturing method of the thin film transistor array panel. The method of claim 1, And the conductive film pattern is a gate wiring or a data wiring. A binder resin including a first novolak resin and a second novolak resin represented by the following Formula 1 or Formula 2; Photosensitive agent containing a diazide compound; And A photoresist composition comprising a solvent. [Formula 1]

Here, R1 to R4 are alkyl groups. [Formula 2]

Here, R1 to R5 are alkyl groups. The method of claim 7, wherein 5 to 30% by weight of the binder resin; 2 to 10 wt% of the photosensitizer; And A photoresist composition comprising the remaining amount of the solvent. The method of claim 7, wherein The first novolac resin includes meta cresol and para cresol, wherein the content ratio of the meta cresol and the para cresol is 30 to 70: 70 to 30 parts by weight, and an average molecular weight is 2,000 to 10,000. The method of claim 9, The second novolak resin represented by Chemical Formula 1 includes meta cresol, para cresol and xyleneol, and the content ratio of the meta cresol, the para cresol and the xyleneol is 30 to 70: 70 to 30 : 1 to 40 parts by weight, the average molecular weight is 2,000 to 10,000 photoresist composition. The method of claim 10, The mixing ratio of the first novolak resin and the second novolak resin is 1 to 80: 99 to 20 photoresist composition. The method of claim 9, The second novolac resin represented by Chemical Formula 2 includes meta cresol, para cresol and trimethylphenyl, and the content ratio of the meta cresol, the para cresol and the trimethylphenyl is 30 to 70: 70 to 30: 1 to 40 parts by weight and an average molecular weight of 2,000 to 10,000 photoresist composition. 13. The method of claim 12, The mixing ratio of the first novolak resin and the second novolak resin is 1 to 80: 99 to 20 photoresist composition. The method of claim 7, wherein The photosensitizers are 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and 2,3,4,4'-tetrahydroxybenzophenone-1,2 A photoresist composition comprising any one selected from the group comprising naphthoquinonediazide-5-sulfonate and a compound represented by the following formula (3), wherein the mixing ratio is 30 to 70:70 to 30. (3)

Wherein R 1 to R 4 are 2-diazo-1-naphthol-5-sulfonyl or hydrogen, and R 5 to R 8 are alkyl or benzyl groups. The method of claim 7, wherein The solvent is propylene glycol methyl ether acetate (PGMEA), ethyl lactate (EL), ethyl cellulose sol acetate (ECA), 2-methoxy ethyl acetate, gamma butyrolactone (GBL), methyl methoxy propionate (MMP ), Ethylbetaethoxypropionate (EEP), propylene glycol monomethyl ether (PGME), normal propyl acetate (nPAC) and normal butyl acetate (nBA) at least any one selected from the group consisting of. The method of claim 7, wherein The photoresist composition further comprises at least one additive selected from the group consisting of colorants, dyes, anti-scratches, plasticizers, adhesion promoters, rate enhancers and surfactants.

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