KR20140032695A - Photoresist composition and patterning method using the same - Google Patents

Photoresist composition and patterning method using the same Download PDF

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KR20140032695A
KR20140032695A KR1020120099315A KR20120099315A KR20140032695A KR 20140032695 A KR20140032695 A KR 20140032695A KR 1020120099315 A KR1020120099315 A KR 1020120099315A KR 20120099315 A KR20120099315 A KR 20120099315A KR 20140032695 A KR20140032695 A KR 20140032695A
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photoresist composition
photoresist
formula
substrate
group
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KR1020120099315A
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Korean (ko)
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신보라
정혜원
한희
김경준
박찬효
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주식회사 엘지화학
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Publication of KR20140032695A publication Critical patent/KR20140032695A/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

The present invention relates to a photoresist composition and a patterning method using the same. The photoresist composition of the present invention can minimize the loss due to side etching to form a fine pattern of excellent linearity and uniform shape. In addition, a photoresist pattern having improved adhesion to a lower substrate, high sensitivity, and heat resistance may be formed.

Description

PHOTORESIST COMPOSITION AND PATTERNING METHOD USING THE SAME {PHOTORESIST COMPOSITION AND PATTERNING METHOD USING THE SAME}

The present invention relates to a photoresist composition and a patterning method using the same. More specifically, the present invention relates to a photoresist composition capable of effective patterning at a high aspect ratio and a patterning method using the same.

Photolithography is a very important process in the manufacture of semiconductor integrated circuits or fine circuits of liquid crystal display devices. The photolithography process is usually carried out in the following steps. First, the photoresist is uniformly applied to the film to be patterned formed on the substrate. This is selectively exposed and developed to form a photoresist pattern, and then the patterned film is wet or dry etched using a patterned photoresist film as a mask to transfer the fine circuit pattern to the photoresist underlying layer, and then unnecessary It proceeds to the process of removing a resist layer with stripping liquid (stripper).

The positive photoresist composition dissolves in the developer after exposure because the exposed portion is decomposed. Accordingly, a desired pattern can be formed by etching the lower film or substrate using the photoresist pattern as a mask for the unexposed portion.

On the other hand, the light emitting device (light emitting device) of the semiconductor device is a semiconductor device that generates light by flowing a current in the forward direction to the PN junction.

Light emitting devices using semiconductors are attracting attention in next-generation lighting equipment applications because they have high efficiency of converting electrical energy into light energy, have a long lifespan of more than 5 to 10 years, and can greatly reduce power consumption and maintenance costs. .

A sapphire substrate is mainly used for the growth of a gallium nitride compound semiconductor for manufacturing a light emitting device. In order to improve light extraction of a light emitting diode device, a pattern of a certain shape is formed on the sapphire surface and an nitride layer is formed thereon. ), A method using Patterned Sapphire Substrate (PSS), which scatters light emitted by irregularities of the substrate surface and improves light extraction efficiency, has been proposed.

1A to 1D are cross-sectional views illustrating a step of forming a patterned sapphire substrate using a photoresist composition.

First, referring to FIG. 1A, a photoresist composition is coated on a sapphire substrate 110 to form a photoresist film 110. Next, the photoresist pattern 110a is formed by selectively exposing and developing the region to which the photoresist composition is applied (FIG. 1B). The lower substrate 110 is etched using the photoresist pattern 110a as a mask (FIG. 1C). Referring to FIG. 1D, a PSS having improved light extraction efficiency may be obtained by peeling the photoresist pattern 110a and etching the pattern into a cone shape.

At this time, as a method for increasing the light extraction efficiency, a method of increasing the depth while maintaining the width of the PSS pattern is used. To this end, the photoresist pattern must also be formed high. As the thickness of the photoresist is increased, it is difficult to secure linearity according to the phenomenon. In addition, there is a problem that the photoresist is reflowed by heat by a heat treatment process before and after exposure, and thus it is difficult to maintain a uniform pattern.

It is an object of the present invention to provide a photoresist composition capable of forming a photoresist pattern having improved adhesion to a substrate, high sensitivity, heat resistance, linearity, and the like.

Still another object of the present invention is to provide a patterning method using the photoresist composition.

The present invention to solve the above problems, novolak-based resin; Photosensitizers comprising a non-benzophenone compound represented by the formula (3); And it provides a photoresist composition comprising an organic solvent.

(3)

Figure pat00001

In Formula 3,

R3 is a direct bond or -CR5R6-;

R4, R5 and R6 are each independently the same or different hydrogen, an alkyl group having 1 to 6 carbon atoms,

Figure pat00002
And
Figure pat00003
It is 1 type selected from the group which consists of;

R 7 is a direct bond or a straight chain or branched alkylene group having 1 to 6 carbon atoms;

Q1 to Q4 are each independently the same or differently hydrogen or diazonaphthoquinone-5-sulfonate.

In another aspect, the present invention comprises the steps of applying the photoresist composition on a substrate or a film to be patterned; Selectively exposing and developing the region to which the photoresist composition is applied to form a photoresist pattern; It provides a patterning method comprising etching the substrate or film using the photoresist pattern as a mask.

The photoresist composition of the present invention can minimize top CD loss due to side etching to form a fine pattern having excellent linearity and uniform shape. In addition, it is possible to solve the problem of the reflow phenomenon during the heat treatment process, it is possible to form a photoresist pattern with improved adhesion to the lower substrate, high sensitivity, heat resistance and the like.

Therefore, by using such a photoresist pattern in an etching mask, various substrates or thin films can be effectively patterned during the manufacturing process of various elements such as liquid crystal display elements or light emitting diode elements. In particular, it can be useful in the process of Patterned Sapphire Substrate (PSS).

1A to 1D are cross-sectional views illustrating a step of forming a patterned sapphire substrate using a photoresist composition.
FIG. 2 is a photograph photographing the photoresist pattern at 10,000 times magnification with a scanning electron microscope before the hard bake process after development in Examples 1 and 2 and Comparative Example 1. FIG.
3 is a photograph taken by magnifying the photoresist pattern after performing the hard bake process in Examples 3, 4 and Comparative Example 2 with a scanning electron microscope 22,000 times.
FIG. 4 is a photograph obtained by magnifying the photoresist pattern after performing the hard bake process in Example 5 and Comparative Example 3 with a scanning electron microscope 15,000 times. FIG.
5 is a photograph taken by enlarging the surface of the ITO layer according to Experimental Examples 1 to 3 by 100 times with an optical microscope.

The photoresist composition of the present invention, a novolak-based resin; Photosensitizers comprising a non-benzophenone compound represented by the formula (3); And organic solvents.

(3)

Figure pat00004

In Formula 3,

R3 is a direct bond or -CR5R6-;

R4, R5 and R6 are each independently the same or different hydrogen, an alkyl group having 1 to 6 carbon atoms,

Figure pat00005
And
Figure pat00006
It is 1 type selected from the group which consists of;

R 7 is a direct bond or a straight chain or branched alkylene group having 1 to 6 carbon atoms;

Q1 to Q4 are each independently the same or differently hydrogen or diazonaphthoquinone-5-sulfonate.

In addition, the patterning method of the present invention comprises the steps of applying the photoresist composition on a substrate or a film to be patterned; Selectively exposing and developing the region to which the photoresist composition is applied to form a photoresist pattern; And etching the substrate or the film using the photoresist pattern as a mask.

In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

Also in the present invention, when each element is referred to as being formed on or "on " each element, it is meant that each element is formed directly on top of each element, It may be additionally formed on the substrate, between the layers, on the object, and on the substrate.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, a photoresist composition and a patterning method according to a specific embodiment of the present invention will be described with reference to the drawings.

Photoresist  Composition

The photoresist composition of the present invention, a novolak-based resin; Photosensitizers comprising a non-benzophenone compound represented by the formula (3); And organic solvents.

(3)

Figure pat00007

In Formula 3,

R3 is a direct bond or -CR5R6-;

R4, R5 and R6 are each independently the same or different hydrogen, an alkyl group having 1 to 6 carbon atoms,

Figure pat00008
And
Figure pat00009
It is 1 type selected from the group which consists of;

R 7 is a direct bond or a straight chain or branched alkylene group having 1 to 6 carbon atoms;

Q1 to Q4 are each independently the same or differently hydrogen or diazonaphthoquinone-5-sulfonate.

Recently, in the photolithography process, the depth of the etching process is gradually increasing. In order to make the depth of the etching process deep and uniform, the photoresist mask layer needs to be formed at a high thickness while maintaining the vertical. To this end, a hard bake process may be further performed before and after exposure in order to improve adhesion and physical strength of the photoresist film. However, as the photoresist is thickly applied, it is not easy to secure linearity due to development and loss due to side etching (CD, Critical Dimension) is likely to occur. In addition, there is a problem in that the photoresist is reflowed by heat by a heat treatment process, thereby making it difficult to maintain a uniform pattern.

According to the photoresist composition of the present invention, the loss due to side etching (TOP CD loss) is minimized to form a pattern having excellent linearity and uniform shape. In addition, due to the improved heat resistance, a reflow phenomenon may be reduced during the heat treatment process, thereby forming a photoresist pattern having improved adhesion to a lower substrate or a film, high sensitivity, heat resistance, linearity, and the like.

According to one embodiment of the present invention, the novolak-based resin may be a resin including a repeating unit represented by the following Chemical Formula 1 or a repeating unit represented by the following Chemical Formula 2. Alternatively, resins containing repeating units represented by the following formulas (1) and (2) may be used in admixture at any ratio.

[Chemical Formula 1]

Figure pat00010

(2)

Figure pat00011

In the above Formulas 1 and 2,

R1, R2 and R2 'are each independently the same or differently hydrogen or an alkyl group having 1 to 6 carbon atoms;

n and m represent the polymerization degree of each repeating unit, and n: m is about 1: 9 to about 5: 5.

The weight average molecular weight (Mw) of the novolac-based resin may be about 5,000 to about 25,000. More specifically, the weight average molecular weight of the resin including the repeating unit represented by Chemical Formula 1 may be about 6,000 to about 10,000, preferably about 8,000 to about 9,000, and includes the repeating unit represented by Chemical Formula 2 The weight average molecular weight of the resin may be about 15,000 to about 25,000, preferably about 20,000 to about 25,000. By using a novolak-based resin having the above-described weight average molecular weight range, the photoresist composition containing the resin exhibits proper solubility and excellent straightness, thereby making it possible to form a good photoresist pattern.

The novolak-based resin may be obtained by condensation reaction of a phenol compound or an aldehyde compound in the presence of an acidic catalyst.

Examples of the phenolic compound include metacresol or para cresol.

Examples of the aldehyde-based compound include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylaldehyde, α- or β-phenylpropylaldehyde, o-, m-, or p-hydroxybenzaldehyde, o -, m-, or p-methylbenzaldehyde etc. are mentioned. These may be used alone or in combination.

According to one embodiment of the present invention, the novolak-based resin may be used by appropriately adjusting the content according to the use and the required viscosity of the final photoresist composition. For example, about 20 parts by weight to about 40 parts by weight, preferably about 25 parts by weight to 35 parts by weight, based on 100 parts by weight of the total photoresist composition. When the novolak-based resin is less than 20 parts by weight, the viscosity of the photoresist composition may be too low to form a photoresist film having a desired thickness. In addition, when the content of the novolak-based resin exceeds 40 parts by weight, the viscosity of the photoresist composition may be too high to coat the photoresist composition on the substrate.

The photoresist composition of the present invention includes a nonbenzophenone-based compound as a photosensitive compound.

The non-benzophenone compound may be represented by the following Formula 3.

(3)

Figure pat00012

In Formula 3,

R3 is a direct bond or -CR5R6-;

R4, R5 and R6 are each independently the same or different hydrogen, an alkyl group having 1 to 6 carbon atoms,

Figure pat00013
And
Figure pat00014
It is 1 type selected from the group which consists of;

R 7 is a direct bond or a straight chain or branched alkylene group having 1 to 6 carbon atoms;

Q1 to Q4 are each independently the same or differently hydrogen or diazonaphthoquinone-5-sulfonate.

In this case, "alkylene" refers to a straight or branched chain saturated divalent hydrocarbon group of 1 to 6 carbon atoms.

In addition, the diazonaptoquinone-5-sulfone group may be represented by the following formula (6).

[Chemical Formula 6]

Figure pat00015

According to an embodiment of the present invention, the compound represented by Chemical Formula 3 includes at least two or more of Q1 to Q4 in a structure, and any one or more of Q1 to Q4 included in Chemical Formula 3 may be diazonaptoquinone- 5-sulfonic group.

The non-benzophenone compound represented by Formula 3 may be, for example, any one of the compounds represented by Formulas 3a to 3f.

[Chemical Formula 3]

Figure pat00016

(3b)

Figure pat00017

[Chemical Formula 3c]

Figure pat00018

(3d)

Figure pat00019

[Formula 3e]

Figure pat00020

[Formula 3f]

Figure pat00021

In Chemical Formulas 3a to 3f, Q1 to Q4 are the same as defined in Chemical Formula 3. In addition, any one or more of Q1 to Q4 included in each compound in Chemical Formulas 3a to 3f may be a diazonaptoquinone-5-sulfon group.

According to an embodiment of the present invention, for example, as the non-benzophenone compound, It may be represented by the following structural formula, these may be used alone or in combination of two or more. However, the present invention is not limited thereto.

Figure pat00022
Figure pat00023
Figure pat00024
Figure pat00025
Figure pat00026
Figure pat00027
Figure pat00028

In the above structural formula, D means a diazonaptoquinone-5-sulfon group.

As shown in the above structural formula, the non-benzophenone-based compound represented by the formula (3) is improved in the photoresist composition because the substituents of the hydroxy group or the diazonaptoquinone-5-sulfon group are evenly positioned within the compound without being unevenly distributed to either side. Linearity You can give it.

According to an embodiment of the present invention, the photoresist composition may further include a benzophenone-based compound as a photosensitizer.

The benzophenone-based compound may be represented by the following formula (4).

[Chemical Formula 4]

Figure pat00029

In Chemical Formula 4, Q5, Q6, Q7, and Q8 may be the same or different from each other independently, any one or more of Q5 to Q8 is a diazonaptoquinone-5-sulfon group, and the others are hydrogen.

According to an embodiment of the present invention, for example, as the benzophenone-based compound, It may be represented by the following structural formula, these may be used alone or in combination of two or more. However, the present invention is not limited thereto.

Figure pat00030
Figure pat00031
Figure pat00032
Figure pat00033
Figure pat00034

In the above structural formula, D means a diazonaptoquinone-5-sulfon group.

When the photosensitizer includes both the non-benzophenone compound and the benzophenone compound, the mixing ratio may be a weight ratio of about 2: 8 to about 8: 2, preferably about 3: 7 to about 7: 3. . When the non-benzophenone compound and the benzophenone compound are included in the weight ratio, the photoresist composition of the present invention may form a photoresist pattern having appropriate sensitivity and improved linearity.

The photosensitizer may be included in an amount of about 1 to about 10 parts by weight, preferably about 3 to about 7 parts by weight, based on 100 parts by weight of the total photoresist composition. When the content of the photosensitizer is less than 1 part by weight, the solubility in the developer in the non-exposed region may be too good, which may cause the residual film ratio of the photoresist to decrease after development. On the other hand, when the photosensitive agent exceeds 10 parts by weight, the sensitivity may be lowered due to the decrease in the solubility of the developer in the exposure area.

The organic solvent included in the photoresist composition is a medium for dissolving the remaining components. Specific examples of the organic solvent include, but are not particularly limited to, propylene glycol methyl ether acetate (PGMEA), ethyl lactate, butyl lactate, butyl acetate, methyl-2-hydroxy Isobutylate (methyl-2-hydroxy-isobutylate), N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide (DMF), or dimethyl sulfoxide (DMSO); You may use the mixed solvent which mixed 2 or more types selected from these. As the solvent, propylene glycol methyl ether acetate (PGMEA) can be preferably used.

The organic solvent may be included in an amount of about 50 to about 75 parts by weight based on 100 parts by weight of the total photoresist composition, and may be included as a residual amount of the novolak-based resin, photoresist, and other additives based on the total weight of the photoresist composition. have. When the weight of the organic solvent is less than about 50 parts by weight, the weight of the novolak-based resin and the photosensitive agent is relatively increased, so that the viscosity of the photoresist composition is high, making it difficult to uniformly apply the photoresist composition onto the substrate. When the content of the organic solvent exceeds about 75 parts by weight, it may be relatively difficult to form a photoresist film having a desired thickness by decreasing the weight of the novolak-based resin and the photosensitive agents and decreasing the viscosity.

According to an embodiment of the present invention, the photoresist composition of the present invention may further include a speed enhancer. By further including the rate enhancer, the photosensitive rate can be more precisely controlled to a desired level.

In this case, the rate enhancer may be represented by the following Formula 5.

[Chemical Formula 5]

Figure pat00035

The rate enhancer may be included in an amount of about 0.1 to about 10 parts by weight, preferably about 0.5 to about 5 parts by weight, based on 100 parts by weight of the total photoresist composition. When the content of the rate enhancer is less than 0.1 part by weight, the effect of sensitivity improvement may be insignificant, and when the photosensitive agent is more than 10 parts by weight, the photosensitive speed may be too fast to control the photosensitive speed of the photoresist composition.

In addition to the above-described components, the photoresist composition may further include additives such as adhesion promoters, surfactants, dyes, etc. to improve the performance of the composition. The content of the additive is not particularly limited to a range capable of improving performance without deteriorating the physical properties of the composition as a whole, for example, about 0.01 to about 0.1 parts by weight based on 100 parts by weight of the total photoresist composition. Can be.

The adhesion promoter is used to improve adhesion between the substrate and the photoresist pattern. For example, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, or the like may be used. . Specific examples of the adhesion promoter include 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane (trade name KBM 303), 3-glycidoxypropyl trimethoxy (trade name KBM 403), 3-aminopropyltrimethoxysilane (trade name KBM 903), hexamethoxymethyl melamine, and the like. . These adhesion promoters may be used alone or in combination of two or more.

By using the photoresist composition of the present invention, the pattern shape is excellent, and reflow phenomenon can be prevented during the heat treatment process. In addition, it is possible to form a photoresist pattern having high adhesion to a lower film or a substrate, high sensitivity and heat resistance, low TOP CD loss, and high aspect ratio. Accordingly, the photoresist composition of the present invention is applied to all processes requiring a photolithography process as well as a substrate etching process such as Patterned Sapphire Substrate (PSS) in a device such as a liquid crystal display (LCD) or a light emitting diode (LED). It can be usefully used.

Patterning  Way

According to another aspect of the present invention, a patterning method is provided.

The patterning method according to the present invention comprises the steps of applying the above-described photoresist composition on a substrate or a film to be patterned; Selectively exposing and developing the region to which the photoresist composition is applied to form a photoresist pattern; And etching the substrate or the film using the photoresist pattern as a mask.

According to an embodiment of the present invention, the patterning target may be a substrate. The substrate may be, for example, a substrate made of sapphire (Al 2 O 3 , sapphire), silicon carbide (SiC), gallium nitride (GaN), zinc oxide (ZnO), aluminum nitride (AlN), or the like. . According to an embodiment of the present invention, the substrate may be a sapphire substrate. Sapphire is a crystalline aluminum oxide, which is chemically and thermally stable, and thus can be manufactured at high temperature, and has a high binding energy and dielectric constant.

According to another embodiment of the present invention, the patterning object may be a layer formed on a substrate.

In order to improve the light extraction degradation of the light emitting diode device, by forming a pattern of a certain shape on the surface of the sapphire substrate and growing a nitride layer thereon, the light emitted by the irregularities of the substrate surface can be scattered to improve the light extraction efficiency This is the Patterned Sapphire Substrate (PSS) process.

According to an embodiment of the present invention, the substrate may be patterned using the photoresist composition described above in the PSS process. According to the patterning method of the substrate using the photoresist composition of the present invention, the pattern shape is excellent, the reflow phenomenon can be prevented during the heat treatment process, the adhesion to the substrate is high, and the sensitivity and heat resistance are high, so the linearity of the pattern is excellent. And a photoresist pattern having a high aspect ratio.

In the patterning method according to the invention, the photoresist composition is a novolak-based resin; Photosensitizers comprising a non-benzophenone compound represented by the formula (3); And organic solvents.

(3)

Figure pat00036

In Formula 3,

R3 is a direct bond or -CR5R6-;

R4, R5 and R6 are each independently the same or different hydrogen, an alkyl group having 1 to 6 carbon atoms,

Figure pat00037
And
Figure pat00038
It is 1 type selected from the group which consists of;

R 7 is a direct bond or a straight chain or branched alkylene group having 1 to 6 carbon atoms;

Q1 to Q4 are each independently the same or differently hydrogen or diazonaphthoquinone-5-sulfon group.

Including the non-benzophenone compound represented by the formula (3), a more detailed description of the photoresist composition is as described above.

The photoresist composition is applied to a substrate or film to be patterned with a thickness of about 2 to about 4 μm, preferably about 2.5 to about 3 μm, using conventional application methods including dipping, spraying, spinning and spin coating. can do.

According to an embodiment of the present invention, soft baking may be performed on the substrate to which the photoresist composition is applied. The soft baking process is a step of applying heat to remove the organic solvent included in the photoresist composition.

Only a desired portion is selectively exposed to a region to which the photoresist composition is applied using a mask pattern or the like. The exposure step is a process of placing a mask pattern between the substrate and the light source, and allowing the light from the light source to pass through only the portion without the pattern to photosensitive the photoresist composition.

Meanwhile, according to an embodiment of the present invention, a heat treatment (pre bake and / or post bake) process may be further performed before and / or after the exposure.

The pre bake process may be performed, for example, at a temperature of about 90 to 120 ° C. for about 40 seconds to 90 seconds, and the post bake process may be, for example, about It may proceed for about 50 seconds to 150 seconds at a temperature of 90 to 130 ℃. Each heat treatment process condition can be adjusted in this range to better form a photoresist pattern.

According to an embodiment of the present invention, the exposing step may be performed using a light source having a wavelength of about 365 to 436 nm, for example, i-line or g-line light. In addition, the exposing step may be performed at an exposure energy of about 30 to 150 mJ / cm 2 , preferably about 80 to 130 mJ / cm 2 . In order to form a photoresist pattern having excellent linearity while maintaining the photoresist layer vertically, an exposure step may be performed under the above exposure energy conditions.

After exposure, the photoresist composition is developed to form a photoresist pattern.

In the developing step, a portion of the photoresist layer, which is relatively weakened through the exposure process, is dissolved using a developer. The substrate including the exposed photoresist film is sufficiently immersed in an alkaline developing aqueous solution, and then left until the exposed photoresist film is dissolved. Although it does not specifically limit as said alkaline developing aqueous solution, The aqueous solution containing alkali hydroxide, ammonium hydroxide, tetramethylammonium hydroxide (TMAH), and (2-hydroxyethyl) trimethyl ammonium hydroxide can be used.

When the exposed part is dissolved and removed, the substrate is removed from the developer, washed, and dried to form a photoresist pattern having a desired shape.

According to an embodiment of the present invention, after the developing and cleaning process, hard baking may be further performed. The hard baking process may be performed, for example, at a temperature of about 100 to 150 ° C. for about 50 seconds to 150 seconds, preferably at about 110 to 140 ° C. for about 60 to 120 seconds.

In the hard baking step, heating to a temperature below the softening point of the photoresist removes moisture remaining on the substrate after development, causes crosslinking by novolak resin molecules in the photoresist, and thus heat resistance of the pattern and the photoresist film. In order to improve adhesion, chemical resistance and physical strength. However, the heat applied during the hard baking process may cause the photoresist to reflow, making it difficult to maintain a uniform pattern. However, the photoresist composition of the present invention exhibits high heat resistance, thereby preventing a reflow phenomenon during the hard baking process, thereby maintaining a uniform pattern shape.

Next, the substrate or film exposed by the photoresist pattern is etched by treating with a corrosion solution or a gas plasma. At this time, the unexposed portion is protected by the photoresist pattern. After etching, the desired pattern is formed on the substrate or the film by removing the photoresist pattern with a suitable stripping solution.

Hereinafter, the present invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example >

Photoresist  Preparation of the composition

Produce Example  One

25 wt% of m-cresol novolac resin (Mw 6,000) of Formula 1, TPPA 320 as a photosensitizer (a nonbenzophenone compound of Formula 3a, where the distribution of substituents satisfies OD / (OH + OD) = 2/3 3.5 wt% of a single compound or mixture), 1.5 wt% of a speed enhancer of Formula 5 and 70 wt% of a solvent (PGMEA) were mixed to prepare a photoresist composition.

Produce Example  2

M435 as a photosensitizer (a single compound or mixture in which the distribution of substituents is a benzophenone-based compound of Formula 4 and satisfying OD / (OH + OD) = 3.5 / 4) A photoresist composition was prepared in the same manner as in Preparation Example 1, except that 1.75 wt% and 1.75 wt% of TPPA 320 were used.

Produce Example  3

17.5% by weight of m-cresol novolac resin (Mw 60,000) of formula (1) and salicylaldehyde novolac resin (Mw 23,000) having n: m of about 3: 7 in formula (2) A photoresist composition was prepared in the same manner as in Preparation Example 1, except that 7.5 wt% was used.

Produce Example  4

10% by weight of the m-cresol novolac resin (Mw 6,000) of formula (1) and salicylaldehyde novolac resin (Mw 23,000) having n: m of about 3: 7 in formula (2) A photoresist composition was prepared in the same manner as in Preparation Example 1, except that 15 wt% was used.

Produce Example  5

1 wt% of 3-glycidoxypropyl trimethoxy (trade name KBM 403) was further mixed with the adhesion promoter in Preparation Example 1 to prepare a photoresist composition.

Produce Example  6

1 wt% of hexamethoxymethyl melamine was further mixed with the adhesion promoter in Preparation Example 1 to prepare a photoresist composition.

Produce Example  7

A photoresist composition was prepared in the same manner as in Preparation Example 1, except that the rate enhancer of Formula 5 was not used.

Produce Comparative Example  One

A photoresist composition was prepared in the same manner as in Preparation Example 1, except that 3.5 wt% of M435 was used as a photosensitizer.

Produce Comparative Example  2

A photoresist composition was manufactured in the same manner as in Preparation Comparative Example 1, except that 1.5 wt% of a novolak-based oligomer PAPS-PN2 (Asahi Organic Chemicals Industry Co., Ltd.) was used instead of the rate enhancer of Chemical Formula 5.

Substrate Patterning  Way

Example  One

The photoresist composition of Preparation Example 1 was spin-coated to a sapphire substrate to a thickness of 2.6 μm, and prebake was performed for 1 minute at a temperature of 110 ° C. before exposure. Afterwards, i-line stepper exposure equipment was used to select a pattern size of 2 μm with an exposure energy of 125 mJ / cm 2 . The exposure was advanced. Subsequently, post-exposure heat treatment (post bake) was performed at a temperature of 110 ° C. for 2 minutes, and developed using a 2.38% TMAH alkali developer to form a photoresist pattern.

After developing and washing with deionized water, a hard bake was performed for 2 minutes at a temperature of 130 ° C.

Using the photoresist pattern as a mask, the sapphire substrate was etched in the form of a cone having a width of 2.6 μm and a depth of 1.5 μm by dry etching.

Example  2

The substrate was patterned in the same manner as in Example 1 except that the photoresist composition of Preparation Example 2 was used.

Example  3

The substrate was patterned in the same manner as in Example 1 except that the photoresist composition of Preparation Example 3 was used.

Example  4

The substrate was patterned in the same manner as in Example 1 except that the photoresist composition of Preparation Example 4 was used.

Example  5

The substrate was patterned in the same manner as in Example 1 except that the pattern was exposed to a size of 5 mu m.

Example  6

The substrate was patterned in the same manner as in Example 1 except that the photoresist composition of Preparation Example 7 was used.

Comparative Example  One

The substrate was patterned in the same manner as in Example 1 except that the photoresist composition of Preparation Comparative Example 1 was used.

Comparative Example  2

The substrate was patterned in the same manner as in Example 1 except that the photoresist composition of Preparation Comparative Example 2 was used.

Comparative Example  3

The substrate was patterned in the same manner as in Comparative Example 1 except that the pattern was exposed to a size of 5 μm.

< Experimental Example >

Pattern shape evaluation

2 shows photographs taken of electron patterns (10,000 magnification) of the pattern after the development in Examples 1 and 2 and Comparative Example 1 before the hard bake process.

Referring to FIG. 2, the pattern formed using the photoresist composition of the present invention showed high aspect ratio and sensitivity. In particular, when comparing Examples 1, 2 and Comparative Example 1 in Figure 2, it can be seen that by using a photosensitive agent containing a non-benzophenone-based compound, TOP CD loss is reduced to show a good linearity.

Heat resistance evaluation

3 shows photographs taken of the patterns obtained by performing the hard bake process in Examples 3, 4 and Comparative Example 2 using an electron microscope (22,000 magnification).

In addition, the photograph obtained by the electron microscope (15,000 magnification) of the pattern obtained after performing the hard bake process in Example 5 and Comparative Example 3 is shown in FIG.

3 and 4, when the photoresist composition of the present invention is used, the phenomenon of reflow due to heat is reduced even after performing the hard bake process, so that the loss of the photoresist pattern is less than that of the comparative example.

Adhesion evaluation

Experimental Example  One

In the photoresist composition according to the present invention, the experiment was carried out as follows to evaluate the adhesion of the composition comprising the adhesion promoter.

The photoresist composition of Preparation Example 5 was spin-coated on the ITO layer to a thickness of 2.6 μm, and then prebakeed for 1 minute at a temperature of 110 ° C. before prebake. Thereafter, exposure was selectively performed using an i-line stepper exposure apparatus as a mask having a dot pattern having a size of 1 to 50 μm with an exposure energy of 125 mJ / cm 2 .

The surface was photographed with an optical microscope to confirm the dot pattern remaining on the ITO layer after development and cleaning after exposure.

Experimental Example  2

Exposure and development were carried out in the same manner as in Experiment 1 using the photoresist composition of Preparation Example 6.

Experimental Example  3

Exposure and development were performed in the same manner as in Experiment 1 using the photoresist composition of Preparation Comparative Example 1.

5 is a photograph taken by expanding the surface of the ITO layer 100 times with an optical microscope after performing Experimental Examples 1 to 3.

Referring to FIG. 5, in Experimental Example 1, a dot pattern having a size of 30 μm or more remained, whereas in Experimental Example 2, a large number of dot patterns having a size of 20 μm or more remained, but in Experimental Example 3, no remaining pattern was observed. Therefore, it can be seen that the adhesion of the photoresist composition of the present invention is excellent.

100: substrate
110: photoresist film
110a: photoresist pattern

Claims (16)

Novolak-based resins; Photosensitizers comprising a non-benzophenone compound represented by the formula (3); And an organic solvent;
(3)
Figure pat00039

In Formula 3,
R3 is a direct bond or -CR5R6-;
R4, R5 and R6 are each independently the same or different hydrogen, an alkyl group having 1 to 6 carbon atoms,
Figure pat00040
And
Figure pat00041
It is 1 type selected from the group which consists of;
R 7 is a direct bond or a straight chain or branched alkylene group having 1 to 6 carbon atoms;
Q1 to Q4 are each independently the same or differently hydrogen or diazonaphthoquinone-5-sulfonate.
The photoresist composition of claim 1, wherein the non-benzophenone compound represented by Formula 3 is selected from the group consisting of compounds represented by Formulas 3a to 3f:
[Chemical Formula 3]
Figure pat00042

(3b)
Figure pat00043

[Chemical Formula 3c]
Figure pat00044

(3d)
Figure pat00045

[Formula 3e]
Figure pat00046

[Formula 3f]
Figure pat00047

In Formulas 3a to 3f, Q1 to Q4 are as defined in Formula 3, and any one or more of Q1 to Q4 included in each compound is a diazonapthoquinone-5-sulfonate. .
The photoresist according to claim 1, wherein the photoresist comprises 20 to 40 parts by weight of the novolac resin, 1 to 10 parts by weight of the photosensitive agent and 50 to 75 parts by weight of the organic solvent, based on 100 parts by weight of the total photoresist composition. Composition.
The photoresist composition of claim 1, further comprising a benzophenone-based compound represented by Formula 4 below:
[Chemical Formula 4]
Figure pat00048

In Formula 4,
In Chemical Formula 4, Q5, Q6, Q7, and Q8 may be the same or different from each other independently, any one or more of Q5 to Q8 is a diazonaptoquinone-5-sulfon group, and the others are hydrogen.
The photoresist composition of claim 4, wherein the photosensitive agent comprises a non-benzophenone compound and a benzophenone compound in a weight ratio of 2: 8 to 8: 2.
The photoresist composition of claim 1, wherein the novolak-based resin comprises any one or more of a resin including a repeating unit represented by Formula 1 or a resin including a repeating unit represented by Formula 2 below:
[Chemical Formula 1]
Figure pat00049

(2)
Figure pat00050

In the above Formulas 1 and 2,
R1, R2 and R2 'are each independently the same or differently hydrogen or an alkyl group having 1 to 6 carbon atoms;
n and m represent the polymerization degree of each repeating unit, and n: m is about 1: 9 to about 5: 5.
The photoresist composition of claim 1, further comprising a rate enhancer.
The photoresist composition of claim 7, wherein the rate enhancer is represented by the following Chemical Formula 5:
[Chemical Formula 5]
Figure pat00051

 The method of claim 1, wherein the organic solvent is propylene glycol methyl ether acetate (PGMEA), ethyl lactate, butyl lactate, butyl acetate, methyl-2-hydroxy isobutylate at least one selected from the group consisting of (methyl-2-hydroxy-isobutylate), N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) Photoresist composition comprising a.
The photoresist composition of claim 1, further comprising an adhesion promoter.
The photoresist composition of claim 1, wherein the adhesion promoter comprises at least one selected from the group consisting of 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane, 3-glycidoxypropyl trimethoxy, 3-aminopropyltrimethoxysilane, and hexamethoxymethyl melamine.
The photoresist composition of claim 1, which is used in a manufacturing process of a liquid crystal display device (LCD) or a light emitting diode device (LED).
Applying the photoresist composition of claim 1 onto a substrate or a film to be patterned;
Selectively exposing and developing the region to which the photoresist composition is applied to form a photoresist pattern; And
Etching the substrate or the film by using the photoresist pattern as a mask.
The method of claim 13, further comprising hard baking after forming the photoresist pattern.
The patterning method of claim 14, wherein the hard baking step is performed at a temperature of 100 to 150 ° C. 15.
The method of claim 13, wherein the substrate is a sapphire substrate.
KR1020120099315A 2012-09-07 2012-09-07 Photoresist composition and patterning method using the same KR20140032695A (en)

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