KR101400390B1 - Photoresist composition and method for manufacturing of organic light emitting display device using the same - Google Patents

Abstract

A photoresist composition according to an embodiment of the present invention comprises a new photoacid generator (PAG); and a perfluoro decyl methacrylate (FDMA) and 2- methyl adamantyl methacrylate (MAMA) copolymer. Accordingly, by introducing the photoresist composition containing the photoacid generator which is selectively dissolved in a perfluorinated solvent, the bad effect from a hydrophilic or hydrophobic solvent can be reduced. Moreover, the photoacid generator shows the lower acidity than the existing ion photoacid generator because of the non-ionic properties (non-ionic PAG) and therefore the acidity of the organic luminous material can be reduced.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a photoresist composition and an organic electroluminescent display device using the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist composition and a method of manufacturing an organic electroluminescence display using the same, and more particularly, to a photoresist composition containing a novel photo- .

The organic light emitting display, which is one of the new flat panel display devices, is a self-luminous type and has a better viewing angle and contrast ratio than a liquid crystal display (LCD), and can be lightweight and thin because of no need for a separate backlight. . In addition, it is possible to drive the DC low voltage, has a high response speed, and is especially advantageous in terms of manufacturing cost.

An organic electroluminescent display device has a structure in which electrons and holes are injected into the light emitting layer from an electron injection electrode (cathode) and a hole injection electrode (anode), respectively, and excitons, And an organic electroluminescent device which emits light when it emits light. In this case, the organic light emitting display device includes a top emission, a bottom emission, and a dual emission according to a direction in which light is emitted. In accordance with a driving method, a passive matrix ) And active matrix (Active Matrix).

Accordingly, when a scan signal, a data signal, a power supply, and the like are supplied to a plurality of subpixels arranged in a matrix form, the organic light emitting display device can display an image by causing the selected subpixel to emit light. At this time, the sub-pixel includes a thin film transistor (TFT) including a switching thin film transistor, a driving thin film transistor and a capacitor, and a first electrode connected to the driving transistor included in the thin film transistor, a light emitting layer and a second electrode.

The organic light emitting display uses a fine metal mask (FMM) method, an ink jetting method, a laser patterning method, or the like to pattern an emission layer (EML) between a first electrode and a second electrode on a substrate. Although this method can manufacture an organic light emitting display capable of realizing a high resolution over a large area, it has a disadvantage in terms of cost and yield in terms of process. Accordingly, a photolithography process capable of realizing a high resolution and a large area has been introduced while considering efficiency.

The photolithography process uses a photosensitive material, and it is important to minimize the damage of the light emitting layer by the photoresist and the photoacid generator (PAG).

Accordingly, there is a need to develop various materials that can minimize the influence on the device performance of an organic light emitting display device.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a photo acid generator capable of minimizing damage to a light emitting layer, a photoresist composition containing the same, and a method of manufacturing an organic light emitting display using the same. .

The photoacid generator according to one aspect of the present invention includes a photo-acid generator (PAG) represented by any one of the following formulas (1) to (4).

According to another aspect of the present invention, there is provided a photoresist composition comprising: a photoacid generator (PAG) represented by any one of Chemical Formulas 1 to 4; And perfluorodecyl methacrylate (FDMA) and 2-methyladamantyl methacrylate (MAMA) copolymers.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

According to another aspect of the present invention, there is provided a method of fabricating an organic light emitting display, including: forming a first electrode on a substrate; Forming a photoresist composition according to an embodiment of the present invention on the first electrode; Patterning the photoresist composition by irradiating ultraviolet rays (UV) through a mask pattern; Forming an organic light emitting layer on the patterned photoresist composition; And removing the patterned photoresist composition and the organic light emitting layer in contact with the top of the patterned photoresist composition.

According to the present invention, by introducing a photoresist composition containing a photoacid generator capable of selectively dissolving in a perfluorinated solvent, adverse effects caused by hydrophilic or hydrophobic solvents can be reduced.

In addition, due to the long absorption wavelength band of the photoacid generator according to an embodiment of the present invention, damage to the device which may occur during the photolithography process can be improved.

In addition, since the photoacid generator according to an embodiment of the present invention has a non-ionic PAG characteristic, it exhibits weaker acidity than conventional ionic photoacid generators. As a result, Can be reduced.

Accordingly, the present invention can provide an organic electroluminescent display device capable of achieving high efficiency, high resolution, and large area through a photoresist composition capable of increasing the degree of fluorination.

1 to 5 are cross-sectional views illustrating a process of manufacturing an organic light emitting display according to an exemplary embodiment of the present invention; And
Figures 6 and 7 are cross-sections illustrating a patterned photoresist composition and a patterned organic light emitting layer.

Embodiments of the present invention will now be described in detail with reference to the accompanying drawings. Like reference numerals throughout the specification denote substantially identical components. In the following description, well-known functions or constructions are not described in detail to avoid unnecessarily obscuring the subject matter of the present invention.

The photoresist composition according to an embodiment of the present invention includes perfluorodecyl methacrylate (FDMA) and 2-methyladamantyl methacrylate (MAMA) copolymer and a photoacid generator (PAG) .

In one embodiment, the photo-acid generator (PAG) may be represented by any one of the following formulas (1) to (4).

The photoacid generator (FMSFDD-NI) of the formula (1) can be represented as follows.

[Chemical Formula 1]

The photoacid generator (FBSFDD-NI) of formula (2) can be represented as follows.

(2)

The photoacid generator (FMSBFDD-BI) of formula (3) can be represented as follows.

(3)

The photoacid generator (FBSBFDD-BI) of formula (4) can be represented as follows.

[Chemical Formula 4]

As described above, the photoacid generators represented by formulas (1) and (2) are characterized by being absorbed at 365 nm, and have high solubility in fluorinated solvents by introducing perfluorinated alkyl chains. The photoacid generators represented by formulas (3) and (4) are characterized by being absorbed at 254 nm, and have high solubility in the fluorinated solvent by introducing the perfluorinated alkyl chain.

In addition, due to the long absorption wavelength band of the photoacid generator according to the embodiment of the present invention, it is possible to prevent damage to the device that may occur during the photolithography process.

In addition, since it has a non-ionic PAG characteristic, it exhibits weaker acidity than conventional ionic photoacid generators, and as a result, the acidity of the organic light emitting material can be reduced.

In one embodiment, perfluorodecyl methacrylate (FDMA) and 2-methyladamantyl methacrylate (MAMA) copolymers may be represented by the following formula (5).

[Chemical Formula 5]

At this time, the copolymer represented by the formula (5) may have a ratio of x: y = 0.1 to 1: 4, preferably x: y = 0.75: 4.

As described above, the copolymer represented by the general formula (5) has a property of being dissolved well in a fluorine-based solvent. At this time, the fluorinating solvent and the photoacid generator can efficiently perform the patterning process only when the mutual action is appropriate.

Accordingly, in the present invention, it is possible to have a high solubility in a fluorine-based solvent through a photoresist composition containing an amphoteric photoacid generator (PAG) and a copolymer, reduce the acidity and prevent damage to the organic luminescent layer .

Hereinafter, a synthesis example of a photoacid generator (PAG) and a production example of a photoresist composition according to an embodiment of the present invention will be described in detail. However, the following Synthesis Examples and Preparation Examples are illustrative of the present invention, but the present invention is not limited thereto.

Synthetic example

1) Preparation of naphthalimide-based photoacid generator (Naphthalimide PAG)

≪ Substance I &

3-hydroxy-1,8-naphthalic anhydride (0.26 g, 1.2 mmol) is added to a round flask equipped with a stirrer, and dissolved in N, N-dimethylformamide (DMF) (3 ml). Then sodium hydride (0.06 g, 2.5 mmol) was added to a small amount of DMF and stirred at 100 ° C for 20 minutes.

Further, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-12-iodododecane (1.1 g, 1.8 mmol) Of DMF, and the mixture was stirred for 5 hours.

Then, the mixture was cooled at room temperature, and then acetic acid and water were mixed at a volume ratio of 1: 5 and slowly added to terminate the reaction.

Finally, the precipitate was filtered off under reduced pressure, washed several times with water and methanol and dried to give material I.

<Substance II>

Substance I (1.2 g, 1.7 mmol) and hydroxyamine hydrochloride (0.18 g, 2.6 mmol) were added to a round flask equipped with a stirrer, then 5 ml of pyridine was added and the mixture was stirred at 100 ° C for 20 minutes.

Subsequently, the reaction solution was cooled at room temperature, and 50 ml of a 2 M HCl aqueous solution was added to terminate the reaction.

Finally, the remaining solid was dissolved in chloroform and then re-precipitated by addition of excess methanol to give a dark yellow substance II.

<FMSFDD-NI>

Trifluorotoluene (7.5 ml) was added to a round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser, and the mixture was heated to 100 ° C.

Then, trifluoromethane sulfonic anhydride (0.12 ml, 0.7 mmol) was added thereto, followed by stirring for one hour. After cooling at room temperature, chloroform (17.5 ml) was added, sodium carbonate aqueous solution (15 w / v%, 35 ml) was added, and stirred rapidly for 20 minutes.

Finally, chloroform (50 ml) and distilled water (50 ml) were added to extract, and a small amount of methylene chloride was added to the remaining solid. After recrystallization, FMSFDD-NI was finally obtained.

<FBSFDD-NI>

Trifluorotoluene (7.5 ml) was added to a round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser, and the mixture was heated to 100 ° C.

Then, nonafluorobutane sulfonic anhydride (0.25 ml, 0.7 mmol) was added and stirred for 1 hour. After cooling at room temperature, chloroform (17.5 ml) was added and aqueous sodium carbonate solution (15 w / v%, 35 ml) And the mixture was rapidly stirred for about 20 minutes.

Finally, chloroform (50 ml) and distilled water (50 ml) were added to extract, and a small amount of methylene chloride was added to the remaining solid, and finally FBSFDD-NI was obtained by recrystallization.

2) Preparation of Benzophenonimine PAG (Benzophenonimine PAG)

&Lt; Substance I &

Sodium hydride (0.11 g, 4.4 mmol) was dissolved in a small amount of DMF and the resulting mixture was stirred at room temperature for 1 hour. And the mixture was stirred at 100 ° C for 20 minutes.

Then, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-12-iodododecane (2.5 g, 4.1 mmol) was added in small portions Of DMF, and the mixture was stirred for 5 hours.

Then, the mixture was cooled at room temperature, and then acetic acid and water were mixed at a volume ratio of 1: 5 and slowly added to terminate the reaction.

Finally, the precipitate was filtered off under reduced pressure, washed several times with water and methanol and dried to give material I.

<Substance II>

Subsequently, substance I (0.7 g, 0.6 mmol) and hydroxyamine hydrochloride (0.06 g, 0.9 mmol) were added to a round flask equipped with a stirrer, and then pyridine was added thereto and stirred at 100 ° C for 3 hours.

Then, the reaction solution was cooled at room temperature, and 25 ml of 2 M HCl aqueous solution was added to terminate the reaction.

Finally, the remaining solid was dissolved in chloroform and then re-precipitated by addition of excess methanol to give a dark yellow substance II.

<FMSBFDD-BI>

Trifluorotoluene (6 ml) was added to a round flask with a mass of material II (0.4 g, 0.3 mmol) and completely dissolved, followed by heating to 100 ° C.

Trifluoromethane sulfonic anhydride (0.15 ml, 0.4 mmol) was then added and stirred for one hour. After cooling at room temperature, chloroform (15 ml) was added, aqueous sodium carbonate solution (15 w / v%, 20 ml) was added, and then stirred rapidly for 20 minutes.

Finally, chloroform (50 ml) and distilled water (50 ml) were added to extract the residue, and a small amount of methylene chloride was added to the remaining solid. After recrystallization, FMSBFDD-BI was finally obtained.

<FBSBFDD-BI>

Trifluorotoluene (6 ml) was added to a round flask with a mass of material II (0.4 g, 0.3 mmol) and completely dissolved, followed by heating to 100 ° C.

Then, nonafluorobutane sulfonic anhydride (0.07 ml, 0.4 mmol) was added thereto, followed by stirring for one hour. After cooling at room temperature, chloroform (15 ml) was added, aqueous sodium carbonate solution (15 w / v%, 20 ml) was added, and then stirred rapidly for 20 minutes.

Finally, chloroform (50 ml) and distilled water (50 ml) were added to extract, and a small amount of methylene chloride was added to the remaining solid, and finally FBSBFDD-NI was obtained by recrystallization.

Manufacturing example

& Lt; Photoresist composition & gt ;

According to one embodiment of the present invention, 0.25 g of a copolymer according to an embodiment of the present invention satisfying perfluorodecyl methacrylate (FDMA): 2-methyladamantyl methacrylate (MAMA) = 4: 0.75 0.0125 g of photoacid generator was added.

1 to 5 are cross-sectional views illustrating a process of fabricating an organic light emitting display according to an exemplary embodiment of the present invention. 6 and 7 are cross-sectional views showing a patterned photoresist composition and a patterned organic light emitting layer.

1, a first electrode 20 is formed on a substrate 10 and then a photoresist composition 30 according to an embodiment of the present invention is formed on the first electrode 20 do.

Specifically, a first electrode 20 is formed of TCTA on a glass substrate 10, and a photoresist composition 30 containing a photoacid generator is formed by spin coating

As shown in FIG. 2, the photoresist composition is patterned by irradiating ultraviolet rays (UV) after disposing a mask.

A mask MA having a desired pattern was disposed and an exposure process was performed by irradiating ultraviolet rays having a wavelength of 365 nm. Accordingly, only a part of the photoresist composition is exposed to the ultraviolet rays according to the pattern of the mask MA, and the portions not exposed to the ultraviolet rays are not affected. That is, the portion exposed to the ultraviolet ray changes into the insoluble photoresist composition (IPR), while the portion not exposed to the ultraviolet ray remains the soluble photoresist composition (SPR).

As shown in FIG. 3, a patterned photoresist composition is formed on the first electrode 20.

Specifically, the exposed photoresist composition (SPR) is removed, and the insoluble photoresist composition (IPR) is removed from the first electrode 20 by exposing the ultraviolet (UV) irradiated photoresist composition to a developing solution containing a perfluorinated solvent. As shown in FIG. Thus, a pattern (see FIG. 6) in which the photoresist composition was patterned on the first electrode 20 was confirmed.

As shown in FIG. 4, an organic light emitting layer 40 is formed on the patterned photoresist composition.

Specifically, when the organic light emitting layer 40 is formed on the patterned photoresist composition, the organic light emitting layer can be formed using the patterned photoresist composition as a mask. Thus, the organic luminescent layer 40 having a desired pattern was formed (see Fig. 7).

As shown in Fig. 5, the patterned photoresist composition and the organic luminescent layer 40, which is in contact with the top of the photoresist composition, are removed.

Specifically, when exposed to a peeling liquid containing a perfluorinated solvent, the remaining patterned photoresist composition and the organic luminescent layer that is in contact with the top of the photoresist composition are removed together, thereby forming an organic luminescent layer (40) is formed.

As described above, a process of patterning an organic light emitting layer using a photoresist composition containing a photoacid generator according to an embodiment of the present invention has been described.

Here, the organic light emitting layer may be formed of an organic light emitting material that emits red, green, or blue light, or an organic light emitting material that emits white light. In particular, in the case of an organic luminescent material that emits white light, a photoresist composition according to an embodiment of the present invention may be used to apply a color filter on an organic luminescent material and to pattern a color filter.

As described above, the photoresist composition according to an embodiment of the present invention can be used not only for patterning the organic luminescent material itself, but also for patterning other materials in contact with the organic luminescent material, have.

It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof.

It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

10: substrate 20: first electrode
30: Photoresist composition 40: Organic light-emitting layer
MA: mask SPR: soluble photoresist composition
IPR: insoluble photoresist composition

Claims (9)

A photo-acid generator (PAG) represented by any one of the following formulas (1) to (4).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

A photoacid generator (PAG) represented by any one of Chemical Formulas 1 to 4 below; And
(FDMA), and 2-methyladamantyl methacrylate (MAMA) copolymer. &Lt; Desc / Clms Page number 13 &gt;
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

3. The method of claim 2,
The perfluorodecyl methacrylate (FDMA) and 2-methyladamantyl methacrylate (MAMA)
Is a copolymer represented by the following formula (5), and has a ratio of x: y = 0.1 to 1: 4.
[Chemical Formula 5]

The method of claim 3,
The copolymer represented by the general formula (5)
x: y = 1: 4.
3. The method of claim 2,
The photo-
Wherein the copolymer has a mass percentage of 0.05 to 0.1 at one time.
Forming a first electrode on the substrate;
Forming the photoresist composition of claim 2 on the first electrode;
Patterning the photoresist composition by irradiating ultraviolet rays (UV) through a mask pattern;
Forming an organic light emitting layer on the patterned photoresist composition; And
And removing the patterned photoresist composition and the organic light emitting layer in contact with the top of the patterned photoresist composition.
The method according to claim 6,
Wherein the step of removing the patterned photoresist composition and the organic luminescent layer brought into contact with the top of the patterned photoresist composition uses a perfluorinated solvent.
The method according to claim 6,
The ultraviolet rays,
Wherein the organic electroluminescent display device has a wavelength of 365 nm.
The method according to claim 6,
After forming the first electrode on the substrate,
Forming a hole transporting layer or a hole injecting layer on the organic light emitting display device.

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