KR20080063922A - Pattern forming process for semiconductor device - Google Patents

Pattern forming process for semiconductor device Download PDF

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KR20080063922A
KR20080063922A KR1020070000529A KR20070000529A KR20080063922A KR 20080063922 A KR20080063922 A KR 20080063922A KR 1020070000529 A KR1020070000529 A KR 1020070000529A KR 20070000529 A KR20070000529 A KR 20070000529A KR 20080063922 A KR20080063922 A KR 20080063922A
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composition
pattern
water
semiconductor device
parts
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KR1020070000529A
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Korean (ko)
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이성구
김태환
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주식회사 하이닉스반도체
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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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67098—Apparatus for thermal treatment

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
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  • Structural Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

A method for forming patterns of semiconductor devices is provided to form effectively micro patterns by enhancing boundary characteristics between RELACS materials and photosensitive film patterns. In a method for forming patterns of semiconductor devices to coat water-soluble materials on photosensitive film patterns, a surface of the photosensitive film patterns(115) is rinsed by using a composition(120) having polymer and water before coating the water-soluble materials on the photosensitive film patterns. At this time, the photosensitive film patterns are formed on a substrate(113) through a lithography process. The surface of the photosensitive film patterns is rinsed using the composition having the polymer and water. After coating RELACS(Resolution Enhancement Lithography Assisted by Chemical Shrink) materials(117) on the rinsed photosensitive film patterns, baking is performed. Then the baked resultant is washed.

Description

반도체 소자의 패턴 형성방법{PATTERN FORMING PROCESS FOR SEMICONDUCTOR DEVICE}Pattern Forming Method of Semiconductor Device {PATTERN FORMING PROCESS FOR SEMICONDUCTOR DEVICE}

도 1은 종래에 RELACS 물질을 이용한 패턴 형성방법을 나타내는 공정 단면도이다.1 is a cross-sectional view illustrating a conventional method of forming a pattern using a RELACS material.

도 2는 종래에 코팅 불량을 나타내는 평면도이다.2 is a plan view showing a coating defect in the prior art.

도 3은 본 발명에 따른 패턴 형성방법을 나타내는 공정 단면도이다.3 is a cross-sectional view illustrating a method of forming a pattern according to the present invention.

도 4는 본 발명에서 코팅 불량 없이 코팅되어 있음을 나타내는 평면도이다.Figure 4 is a plan view showing that the coating in the present invention without coating failure.

<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>

13, 113 : 기판 15, 115 : 감광막 패턴13, 113: substrate 15, 115: photoresist pattern

17, 117 : RELACS 물질 18, 118 : 최종 패턴17, 117: RELACS material 18, 118: the final pattern

19 : 가교 결합 120 : 본 발명의 수용성 조성물 층19 crosslinked 120 water soluble composition layer of the present invention

본 발명은 반도체 소자의 패턴 형성방법에 관한 것이다.The present invention relates to a method of forming a pattern of a semiconductor device.

최근 반도체 장치의 제조 기술의 발달과 메모리 소자의 응용 분야가 확장되어 감에 따라 집적도가 향상된 메모리 소자를 개발하기 위하여, 리소그라피 공정의 발전 즉, 감광막의 개발, 새로운 노광원의 개발 및 노광 장비의 개발 등이 가속화되고 있다. 하지만, 현재 상용화되고 있는 KrF 및 ArF 노광 장비를 이용해 얻어지는 해상도는 0.1㎛ 정도로 한정되어 있기 때문에, 이보다 적은 크기의 패턴을 형성하여 고집적화된 반도체 소자를 제조하고자 하는 시도가 계속되고 있다.With the recent development of semiconductor device manufacturing technology and application of memory devices, the development of lithography processes, that is, development of photoresist films, development of new sources of exposure, and development of exposure equipment have been developed to develop memory devices with improved integration. The back is accelerating. However, since the resolution obtained using KrF and ArF exposure equipment, which are currently commercially available, is limited to about 0.1 μm, attempts to manufacture highly integrated semiconductor devices by forming patterns having smaller sizes are continuing.

미세 패턴을 형성하기 위한 방법 중 하나로서 RELACS (Resolution Enhancement Lithography Assisted by Chemical Shrink) 물질을 이용하여 패턴 간 간격을 축소하는 방법이 있다.As one of methods for forming a fine pattern, there is a method of reducing the spacing between patterns using a RELACS (Resolution Enhancement Lithography Assisted by Chemical Shrink) material.

RELACS 물질이란 AZ Electronic Materials사에서 라이선스를 가지고 상품화하고 있는 물질로, 주로 콘택홀의 크기를 축소시키는 공정에 사용되고 있다, 구체적으로, 기판 (13) 위에 노광 공정과 현상 공정을 실시하여 감광막 패턴 (15)을 형성한 다음 (도 1a 참조), 감광막 패턴의 전면에 상기 RELACS 물질 (17)을 코팅하고 가열 공정을 수행하면 상기 RELACS 물질 (17)과 감광막 패턴 (15) 간의 가교 반응 (19)이 일어난다 (도 1b 참조). 이에, 최종적으로 얻어진 패턴 (18)에 의해 패턴간 간격이 축소되므로 콘택홀의 크기를 감소시킨다 (도 1c 참조).RELACS material is a material commercialized under license from AZ Electronic Materials, and is mainly used for the process of reducing the size of contact holes. Specifically, the photoresist pattern 15 is subjected to an exposure process and a development process on the substrate 13. After forming (see FIG. 1A), coating the RELACS material 17 on the entire surface of the photoresist pattern and performing a heating process results in a crosslinking reaction 19 between the RELACS material 17 and the photoresist pattern 15 ( 1b). As a result, the distance between the patterns is reduced by the finally obtained pattern 18, thereby reducing the size of the contact hole (see FIG. 1C).

그러나 감광막이 유기막으로 소수성이 강한데 비하여, RELACS 물질은 수용성이므로 도 2와 같이, RELACS 물질 (17)이 감광막에 제대로 코팅되지 않는 코팅 불량이 발생하게 되어, 실질적으로는 도 1c와 같은 패턴이 얻어지기 곤란하다.However, since the photoresist film is highly hydrophobic as the organic film, since the RELACS material is water-soluble, coating defects in which the RELACS material 17 is not properly coated on the photoresist film are generated as shown in FIG. It is hard to lose.

본 발명의 목적은 리소그라피 공정의 패턴 축소 과정에서 생길 수 있는 코팅 불량을 방지할 수 있는 패턴 형성방법을 제공하는 것이다.An object of the present invention is to provide a pattern forming method that can prevent coating defects that may occur in the pattern reduction process of the lithography process.

상기 목적을 달성하기 위하여 본 발명에서는 감광막 패턴 상부에 RELACS 물질과 같은 수용성 물질을 코팅하기 전에 패턴 상부를 하기 표면 장력이 낮은 용액으로 린스 처리하여 수용성 물질의 코팅 특성을 향상시킬 수 있는 방법을 제공한다.In order to achieve the above object, the present invention provides a method of improving the coating properties of a water-soluble material by rinsing the upper part of the pattern with a solution having a low surface tension before coating the water-soluble material such as RELACS material on the photoresist pattern. .

본 발명에서는 감광막 패턴 위에 수용성 물질을 코팅하는 단계를 포함하는 반도체 소자의 패턴 형성방법에 있어서,In the present invention, in the method of forming a pattern of a semiconductor device comprising the step of coating a water-soluble material on the photosensitive film pattern,

감광막 패턴 위에 수용성 물질을 코팅하기 전에 감광막 패턴 표면을 하기 화학식 1의 중합체와 물을 포함하는 조성물로 린스 처리하는 것을 특징으로 하는 반도체 소자의 패턴 형성방법을 제공한다.Provided is a method of forming a pattern of a semiconductor device, wherein the surface of the photoresist pattern is rinsed with a composition comprising a polymer of Formula 1 and water before coating the water-soluble material on the photoresist pattern.

[화학식 1][Formula 1]

Figure 112007000628579-PAT00002
Figure 112007000628579-PAT00002

상기 식에서, Where

R은 수소 또는 C1~C20의 알킬이며,R is hydrogen or alkyl of C 1 to C 20 ,

m은 0~100 이고, n은 10~300의 정수이다.m is 0-100, n is an integer of 10-300.

이때, 상기 화학식 1에서 R은 메틸, 에틸, 프로필, 부틸, 옥틸, 옥틸 페닐, 노닐, 노닐 페닐, 데실, 데실 페닐, 운데실, 운데실페닐, 도데실 및 도데실 페닐로 이루어진 군으로부터 선택된다.In the above Formula 1, R is selected from the group consisting of methyl, ethyl, propyl, butyl, octyl, octyl phenyl, nonyl, nonyl phenyl, decyl, decyl phenyl, undecyl, undecylphenyl, dodecyl and dodecyl phenyl. .

상기 조성물은 조성물 100 중량부에 대하여 0.0001∼5 중량부의 화학식 1의 화합물과 잔량의 물을 포함하는 것이 바람직하다. 상기 화학식 1의 화합물이 0.0001 중량부 미만으로 첨가되면 코팅 효과가 미미하고, 5 중량부를 초과하여 첨가되면 코팅이 두꺼워져서 패턴 축소(shrink)가 잘 되지않는 단점이 있다.The composition preferably contains 0.0001 to 5 parts by weight of the compound of formula 1 and the remaining amount of water based on 100 parts by weight of the composition. If the compound of Formula 1 is added below 0.0001 parts by weight, the coating effect is insignificant, and if it is added in excess of 5 parts by weight, the coating becomes thick, and thus the pattern shrinkage is not good.

또한, 상기 조성물은 부탄올, 펜탄올, 헥산올 등의 C4~C10의 1차 알코올을 더 포함하여 사용할 수 있다. 이때, 알코올 화합물은 조성물 100 중량부에 대하여 0 초과 10 중량부 이하, 바람직하게는 0.0001~10 중량부로 더 포함된다.In addition, the composition may be used further comprising a C 4 ~ C 10 primary alcohol, such as butanol, pentanol, hexanol. At this time, the alcohol compound is further included in more than 0 to 10 parts by weight, preferably 0.0001 to 10 parts by weight based on 100 parts by weight of the composition.

상기 수용성 물질은 RELACS 물질인 것이 바람직하다.Preferably, the water soluble material is a RELACS material.

상기 본 발명의 방법은 구체적으로 하기와 같은 단계를 포함한다:The method of the present invention specifically includes the following steps:

리소그라피 공정에 의해 기판 위에 감광막 패턴을 형성하는 단계와,Forming a photoresist pattern on the substrate by a lithography process;

감광막 패턴 표면을 상기 화학식 1의 중합체와 물을 포함하는 조성물로 린스 처리하는 단계와,Rinsing the photoresist pattern surface with a composition comprising the polymer of Formula 1 and water;

상기 린스 처리된 패턴 상부에 RELACS 물질을 도포한 후 베이크하는 단계와,Baking and then applying a RELACS material on the rinsed pattern;

상기 결과물을 세정하는 단계.Washing the result.

상기 화학식 1의 화합물은 표면 장력이 낮은 화합물로서 감광막과 RELACS 물질 사이에서 계면의 코팅 특성을 향상시켜주는 역할을 한다.The compound of Formula 1 serves to improve the coating properties of the interface between the photoresist and the RELACS material as a low surface tension compound.

상기 본 발명의 공정을 도면을 참조하여 구체적으로 설명한다.The process of the present invention will be described in detail with reference to the drawings.

기판 (113) 위에 노광 공정과 현상 공정을 실시하여 감광막 패턴 (115)을 형성한 다음 (도 3a 참조), 감광막 패턴의 전면에 상기 화학식 1의 중합체와 물을 포함하는 조성물 (120)로 린스처리를 수행한다 (도 3b 참조). 상기 린스 처리 후, 건조 공정을 수행한다.An exposure process and a development process are performed on the substrate 113 to form a photoresist pattern 115 (see FIG. 3A), and then rinsed with a composition 120 including the polymer of Formula 1 and water on the entire surface of the photoresist pattern. (See FIG. 3B). After the rinse treatment, a drying process is performed.

이와 같은 린스 처리에 의해 감광막 (115) 표면에는 상기 수용성 조성물 층 (120)이 얇게 남게 되고, 이 상부에 RELACS 물질 (117)을 코팅하면 상기 수용성 조성물 (120)에 의해 RELACS 물질의 코팅 특성이 매우 좋게 된다 (도 3c 및 도 4 참조).Such a rinse treatment leaves the water-soluble composition layer 120 thin on the surface of the photoresist film 115, and when the RELACS material 117 is coated thereon, the coating property of the RELACS material is very high by the water-soluble composition 120. Good (see FIGS. 3C and 4).

RELACS 물질 코팅 후에 가열 공정을 수행하면 상기 RELACS 물질 (117)과 감광막 패턴 (115) 간의 가교 반응이 일어나게 되어 최종적으로 얻어진 패턴 (118)에 의해 패턴간 간격이 축소되므로 콘택홀의 크기를 감소시킨다 (도 3d 참조).When the heating process is performed after the coating of the RELACS material, a crosslinking reaction occurs between the RELACS material 117 and the photoresist pattern 115, thereby reducing the size of the contact hole because the interval between the patterns is reduced by the finally obtained pattern 118 (FIG. 3d).

즉, 상기 화학식 1의 화합물을 포함한 조성물을 이용하여 RELACS 물질 코팅 전에 간단한 린스 처리 공정을 처리하면 계면활성제가 코팅되었을 때와 같은 역할을 수행하여 감광막 계면의 상호작용을 증가시키기 때문에, 감광막 표면이 소수성에서 친수성기로 변하게 되어 친수성 성질인 RELACS 물질과 매칭(matching)이 잘 되어 코팅 특성이 좋아지게 된다. That is, if the simple rinse treatment process before the coating of the RELACS material using the composition containing the compound of Formula 1 performs the same role as when the surfactant is coated to increase the interaction of the photoresist interface, the surface of the photoresist film is hydrophobic It becomes a hydrophilic group at and the matching properties with the hydrophilic RELACS material is well (matching) to improve the coating properties.

본 발명의 바람직한 실시예는 예시의 목적을 위한 것으로, 당업자라면 첨부된 특허청구범위의 기술적 사상과 범위를 통해 다양한 수정, 변경, 대체 및 부가가 가능할 것이며, 이러한 수정 변경 등은 이하의 특허청구범위에 속하는 것으로 보아야 할 것이다.Preferred embodiments of the present invention are for the purpose of illustration, and those skilled in the art will be able to make various modifications, changes, substitutions and additions through the spirit and scope of the appended claims, and such modifications may be made by the following claims. Should be seen as belonging to.

이상에서 살펴본 바와 같이, 본 발명에서와 같이 표면 장력이 낮은 물질을 포함하는 용액으로 감광막 표면을 린스하는 공정을 수행하면 추후 패턴 축소 공정을 진행할 때 수용성 물질인 RELACS 물질과 감광막 패턴 사이의 계면 특성이 향상되어 보다 효율적으로 미세 패턴을 형성할 수 있다.As described above, when the process of rinsing the surface of the photoresist film with a solution containing a material having a low surface tension as in the present invention, the interface characteristics between the water-soluble material RELACS material and the photoresist pattern when the pattern reduction process is performed later It can improve and form a fine pattern more efficiently.

Claims (8)

감광막 패턴 위에 수용성 물질을 코팅하는 단계를 포함하는 반도체 소자의 패턴 형성방법에 있어서,In the pattern forming method of a semiconductor device comprising the step of coating a water-soluble material on the photosensitive film pattern, 감광막 패턴 위에 수용성 물질을 코팅하기 전에 감광막 패턴 표면을 하기 화학식 1의 중합체와 물을 포함하는 조성물로 린스 처리하는 것을 특징으로 하는 반도체 소자의 패턴 형성방법: Method of forming a pattern of a semiconductor device, characterized in that the surface of the photoresist pattern is rinsed with a composition comprising a polymer of formula (1) and water before coating the water-soluble material on the photoresist pattern: [화학식 1][Formula 1]
Figure 112007000628579-PAT00003
Figure 112007000628579-PAT00003
 상기 식에서, Where R은 수소 또는 C1~C20의 알킬이며,R is hydrogen or alkyl of C 1 to C 20 , m은 0~100 이고, n은 10~300의 정수이다.m is 0-100, n is an integer of 10-300. 제1항에 있어서,The method of claim 1, 상기 조성물은 조성물 100 중량부에 대하여 0.0001~5 중량부의 화학식 1의 화합물과 잔량의 물을 포함하는 것을 특징으로 하는 반도체 소자의 패턴 형성방법.The composition is a pattern forming method of a semiconductor device characterized in that it comprises 0.0001 to 5 parts by weight of the compound of the formula (1) and the residual amount of water with respect to 100 parts by weight of the composition. 제1항에 있어서,The method of claim 1, 상기 수용성 물질은 RELACS 물질인 것을 특징으로 하는 반도체 소자의 패턴 형성방법.The water-soluble material is a pattern forming method of a semiconductor device, characterized in that the RELACS material. 제1항에 있어서,The method of claim 1, 상기 조성물은 C4~C10의 1차 알코올을 더 포함하는 것을 특징으로 하는 반도체 소자의 패턴 형성방법.The composition is a pattern forming method of a semiconductor device characterized in that it further comprises a C 4 ~ C 10 primary alcohol. 제4항에 있어서,The method of claim 4, wherein 상기 알코올은 조성물 100 중량부에 대하여 0 초과 10이하의 중량부로 포함되는 것을 특징으로 하는 반도체 소자의 패턴 형성방법.The alcohol is a pattern forming method of a semiconductor device, characterized in that contained in more than 0 to 10 parts by weight based on 100 parts by weight of the composition. 제1항에 있어서, 상기 방법은The method of claim 1 wherein the method is 리소그라피 공정에 의해 기판 위에 감광막 패턴을 형성하는 단계와,Forming a photoresist pattern on the substrate by a lithography process; 감광막 패턴 표면을 상기 화학식 1의 중합체와 물을 포함하는 조성물로 린스 처리하는 단계와,Rinsing the photoresist pattern surface with a composition comprising the polymer of Formula 1 and water; 상기 린스 처리된 패턴 상부에 RELACS 물질을 도포한 후 베이크하는 단계와,Baking and then applying a RELACS material on the rinsed pattern; 상기 결과물을 세정하는 단계를 포함하는 반도체 소자의 패턴 형성방법.The pattern forming method of a semiconductor device comprising the step of washing the result. 제6항에 있어서,The method of claim 6, 상기 조성물은 조성물 100 중량부에 대하여 0.0001~5 중량부의 화학식 1의 화합물과 잔량의 물을 포함하는 것을 특징으로 하는 반도체 소자의 패턴 형성방법.The composition is a pattern forming method of a semiconductor device characterized in that it comprises 0.0001 to 5 parts by weight of the compound of the formula (1) and the residual amount of water with respect to 100 parts by weight of the composition. 제6항에 있어서,The method of claim 6, 상기 조성물은 조성물 100 중량부에 대하여 0∼10 중량부의 C4~C10의 1차 알코올을 더 포함하는 것을 특징으로 하는 반도체 소자의 패턴 형성방법.The composition further comprises a 0 to 10 parts by weight of C 4 ~ C 10 primary alcohol with respect to 100 parts by weight of the composition.
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