KR20030049198A - Forming method of photoresist pattern improving etching resistance by relacs material - Google Patents

Forming method of photoresist pattern improving etching resistance by relacs material Download PDF

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KR20030049198A
KR20030049198A KR1020010079350A KR20010079350A KR20030049198A KR 20030049198 A KR20030049198 A KR 20030049198A KR 1020010079350 A KR1020010079350 A KR 1020010079350A KR 20010079350 A KR20010079350 A KR 20010079350A KR 20030049198 A KR20030049198 A KR 20030049198A
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photoresist pattern
photoresist
pattern
relacs
forming method
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KR1020010079350A
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KR100843888B1 (en
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공근규
정재창
이근수
이성구
서형석
신기수
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주식회사 하이닉스반도체
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    • 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
    • H01L21/0274—Photolithographic processes
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Abstract

PURPOSE: A forming method of photoresist pattern improving etching resistance by RELACS(Resist Enhancement Lithography Assisted by Chemical Shrink) material is provided to be capable of improving the etching characteristics of the photoresist pattern. CONSTITUTION: A photoresist layer is formed on the upper portion of an etching object layer. The first photoresist pattern is formed by selectively exposing and developing the photoresist layer. After coating RELACS material on the photoresist pattern, the resultant structure is annealed. The second photoresist pattern is formed by developing the resultant structure. Preferably, the annealing process is carried out at the temperature of 90-150 °C.

Description

Ｒｅｌａｃｓ 물질을 이용하여 식각 내성이 향상된 포토레지스트 패턴을 형성하는 방법{Forming method of photoresist pattern improving etching resistance by RELACS material}Forming method of photoresist pattern improving etching resistance by RELACS material}

본 발명은 Relacs (resist enhancement lithography assisted by chemical shrink) 물질을 이용하여 포토레지스트의 식각 특성을 향상시키는 방법에 관한 것으로, 보다 상세하게는 이미 형성된 포토레지스트 패턴에 Relacs 물질을 도포한 후가열하고 다시 현상함으로써 식각 내성이 향상된 포토레지스트 패턴을 형성하는 방법에 관한 것이다.The present invention relates to a method of improving the etching characteristics of a photoresist by using a relacs (resist enhancement lithography assisted by chemical shrink) material. The present invention relates to a method of forming a photoresist pattern having improved etching resistance.

100nm 이하의 초미세 회로를 사용한 4G DRAM 또는 16G DRAM 제조에 있어서, 패턴이 미세화 됨에 따라 포토레지스트의 두께가 얇아져야 패턴 형성이 가능하다. 포토레지스트 패턴은 하부막 식각 공정시에 일정한 두께를 유지해야 하는데 패턴의 두께가 얇아지면 이것이 곤란해지므로, 포토레지스트가 가져야 할 필수조건은 식각 내성이다. 그러나 이 식각 내성의 극복은 사실상 매우 곤란하다. 즉, 고집적화되는 디바이스에서는 식각 선택비가 높은 감광제 사용이 필수적인데, 현재 상용화되고 있는 ArF 광원용 감광제는 옥사이드 막에 대한 식각 선택비가 낮아 종래의 방법으로 패턴을 형성하면, 도 5에서 볼 수 있는 바와 같이 옥사이드 식각이 곤란하다는 문제가 발생한다.In manufacturing 4G DRAM or 16G DRAM using an ultra-fine circuit of 100 nm or less, as the pattern becomes finer, the thickness of the photoresist must be thinner to form the pattern. The photoresist pattern should be maintained at a constant thickness during the lower layer etching process. When the thickness of the pattern becomes thin, this becomes difficult, so the essential condition for the photoresist is etching resistance. However, overcoming this etch resistance is actually very difficult. That is, in a highly integrated device, the use of a photoresist having a high etching selectivity is essential. A photoresist for ArF light sources, which is currently commercialized, has a low etching selectivity for an oxide film to form a pattern by a conventional method, as shown in FIG. 5. The problem arises that oxide etching is difficult.

이에 본 발명자들은 포토레지스트의 식각 특성을 향상시키기 위하여 노력하여 오던 중, 형성된 포토레지스트 패턴에 Relacs 물질을 도포하면 옥사이드 식각이 가능하다는 점을 알아내어 본 발명을 완성하였다.Accordingly, the present inventors have completed the present invention by finding that oxide etching is possible by applying a Relacs material to the formed photoresist pattern while trying to improve the etching characteristics of the photoresist.

본 발명의 목적은 Relacs 물질을 이용하여 포토레지스트의 식각 특성을 향상시키는 방법을 제공하는 것이다.It is an object of the present invention to provide a method of improving the etching properties of a photoresist using a Relacs material.

도 1은 본 발명의 공정을 나타낸 개요도.1 is a schematic diagram illustrating a process of the present invention.

도 2는 실시예 1에서, Relacs 물질을 도포하기 전에 형성된 패턴 사진.FIG. 2 is a pattern photograph formed in Example 1 before applying the Relacs material. FIG.

도 3은 실시예 1에서, Relacs 물질을 도포하여 가열한 후 현상하여 형성된 패턴 사진.Figure 3 is, in Example 1, a pattern photo formed by coating and heating after applying the Relacs material.

도 4는 도 3에서 형성된 패턴을 식각 마스크로 하여 옥사이드를 식각한 결과를 나타낸 사진.Figure 4 is a photograph showing the result of etching the oxide using the pattern formed in Figure 3 as an etching mask.

도 5는 종래의 방법으로 형성된 포토레지스트 패턴으로 옥사이드를 식각한 결과를 나타낸 사진.Figure 5 is a photograph showing the result of etching the oxide with a photoresist pattern formed by a conventional method.

상기 목적을 달성하기 위하여 본 발명에서는 이미 형성된 포토레지스트 패턴에 Relacs 물질을 도포한 후 가열하고 다시 현상함으로써 식각 내성이 향상된 포토레지스트 패턴을 형성하는 방법을 제공한다.In order to achieve the above object, the present invention provides a method of forming a photoresist pattern having improved etching resistance by applying a relacs material to a photoresist pattern already formed, followed by heating and re-developing.

Relacs (resist enhancement lithography assisted by chemical shrink) 물질이란, 클라리언트 (Clariant)사에서 라이선스를 가지고 상품화하고 있는 물질로서, 주로 콘택홀의 크기를 축소시키는 공정에 사용되고 있다 (Laura J. Peters, "Resist Join the Sub-λ Revolution",Semiconductor International,Sep. 1999; Toshiyuki Toyoshima, "0.1㎛ Level contact hole pattern formation with KrF lithography by Resist Enhancement Lithography Assisted by Chemical Shrink", IEEE, 1998). 본 발명에서는 이러한 Relacs 물질을 이용하여 포토레지스트 패턴의 식각 특성을 향상시키고자 한다.Relacs (resist enhancement lithography assisted by chemical shrink) is a material commercially licensed by Clariant and is used in the process of reducing the size of contact holes (Laura J. Peters, "Resist Join the Sub -λ Revolution ", Semiconductor International, Sep. 1999; Toshiyuki Toyoshima," 0.1 μm Level contact hole pattern formation with KrF lithography by Resist Enhancement Lithography Assisted by Chemical Shrink ", IEEE, 1998). In the present invention, by using the Relacs material to improve the etching characteristics of the photoresist pattern.

이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에서는 Relacs 물질을 이용하여 포토레지스트의 식각 특성을 향상시키는 방법을 제공하는데, 구체적으로,The present invention provides a method of improving the etching characteristics of the photoresist using a Relacs material, specifically,

(a) 피식각층 상부에 포토레지스트 막을 형성하는 단계;(a) forming a photoresist film on the etched layer;

(b) 상기 포토레지스트 막을 선택적으로 노광 및 현상하여 1차 포토레지스트 패턴을 형성하는 단계;(b) selectively exposing and developing the photoresist film to form a primary photoresist pattern;

(c) 상기 포토레지스트 패턴에 Relacs 물질을 도포하여 가열하는 단계; 및(c) applying and heating a Relacs material on the photoresist pattern; And

(d) 상기 (c) 단계의 결과물을 현상하여 1차 포토레지스트 패턴의 가장자리에 Relacs 물질과의 가교 결합이 형성된 2차 패턴을 형성하는 단계를 포함하는 포토레지스트 패턴 형성방법을 제공한다.(d) developing the resultant of step (c) to provide a photoresist pattern forming method comprising forming a secondary pattern having crosslinks formed with a Relacs material on the edge of the primary photoresist pattern.

상기 (a) 및 (b) 단계는 기존의 패턴 형성방법에 의하여 포토레지스트 패턴을 형성하는 과정으로서 [도 1의 (a) 및 (b) 참조], 상기 (b) 단계의 노광전에 소프트 베이크 공정을 수행하고, 노광후에 포스트 베이크 공정을 수행하는 단계를 더 포함할 수 있다.Step (a) and (b) is a process of forming a photoresist pattern by the existing pattern forming method [see (a) and (b) of Figure 1], the soft bake process before the exposure of the step (b) The method may further include performing a post bake process after the exposure.

상기 (c) 및 (d) 단계는 본 발명에 의해 새로 도입된 단계인데, Relacs 물질은 수용성이기 때문에 (b)에서 형성된 패턴 위에 도포가 가능하다. 도포가 끝난 후 가열하면 감광제의 가장자리에 남아있는 산이 Relacs 물질쪽으로 확산되어 Relacs 물질과 감광제 사이에서 일부가 가교반응을 일으킨다 [도 1의 (c) 참조]. 이때 산이 확산된 거리만큼 포토레지스트 수지와 Relacs 물질간의 가교반응이 일어나는데, 온도에 따라 산의 확산 거리가 다르므로 이에 따라 가교되는 면적이 결정되게 된다. 현상시, 미가교 상태의 수용성 물질인 Relacs 물질은 용해되어 없어지게 되고, 상기 가교 부위는 용해되지 않고 남게 되어 상기 (b) 단계에서 형성된 1차 패턴보다 가교부위만큼 CD가 커진 2차 패턴이 형성되는 것이다 [도 1의 (d) 참조]. 한편, 상기 (c) 단계의 가열 온도는 90∼150℃인 것이 바람직하다.Steps (c) and (d) are newly introduced by the present invention. Since the relacs material is water-soluble, it is possible to apply the pattern on the pattern formed in (b). After application, heating causes the acid remaining at the edge of the photosensitive agent to diffuse toward the Relacs material, causing a partial crosslinking reaction between the Relacs material and the photosensitive agent (see FIG. 1 (c)). At this time, the crosslinking reaction between the photoresist resin and the relacs material occurs as much as the acid diffusion distance. Since the diffusion distance of the acid varies depending on the temperature, the crosslinking area is determined accordingly. At the time of development, the relacs material, which is an uncrosslinked water-soluble substance, is dissolved and disappeared, and the crosslinking site remains insoluble and forms a secondary pattern in which the CD is larger by the crosslinking site than the first pattern formed in step (b). [Refer to FIG. 1 (d)]. On the other hand, the heating temperature of the step (c) is preferably 90 ~ 150 ℃.

본 발명의 패턴 형성방법에 사용되는 감광제, 즉 포토레지스트 조성물은 어느 것이나 가능하나, 특히 광산발생제 또는 열산발생제를 포함하는 포토레지스트 조성물이 바람직하고, 포토레지스트 조성물 내의 베이스 수지는 특히 사이클로올레핀 백본(back bone) 구조를 갖는 것으로서, 소정의 기능기(functional group), 예를 들어, 용해억제기로 작용하는 산에 민감한 보호기 및 카르복실산 등의 기능기를 갖는 사이클로올레핀계 공단량체들이 부가 중합된 사이클로 올레핀 백본의 고리(ring) 구조가 깨지지 않고 주쇄 내에 유지되어 있는 반복단위체를 포함하는것이 바람직하며, 보다 바람직하게는 기판 접착성 및 민감성 조절을 위한 히드록시 알킬 기능기를 갖는 사이클로 올레핀 공단량체를 포함하는 것이 좋다.Any photosensitive agent, i.e. photoresist composition, used in the pattern forming method of the present invention can be any one, but a photoresist composition including a photoacid generator or a thermal acid generator is particularly preferable, and the base resin in the photoresist composition is particularly a cycloolefin backbone. As a back bone structure, a cycloolefin-based comonomer having a predetermined functional group, for example, an acid-sensitive protecting group and a functional group such as carboxylic acid, acting as a dissolution inhibiting group is added to a cyclo It is preferable to include repeating units in which the ring structure of the olefin backbone is maintained in the main chain without breaking, and more preferably includes a cycloolefin comonomer having a hydroxy alkyl functional group for controlling substrate adhesion and sensitivity. It is good.

즉, 기판에 대한 접착성을 향상시키기 위하여 2-히드록시에틸 바이사이클로[2.2.1]헵트-5-엔-2-카르복실레이트 또는 2-히드록시에틸 바이사이클로[2.2.2]옥트-5-엔-2-카르복실레이트 공단량체를 포함하는 것이 바람직하고, 예를 들어 하기 화학식 1의 중합반복단위를 포함하는 베이스 수지를 포함할 수 있다.That is, 2-hydroxyethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate or 2-hydroxyethyl bicyclo [2.2.2] oct-5 to improve adhesion to the substrate. It is preferable to include -ene-2-carboxylate comonomer, for example, it may include a base resin containing a polymer repeating unit of the formula (1).

[화학식 1][Formula 1]

상기 식에서,Where

X1, X2, Y1, Y2, Z1및 Z2는 각각 CH2또는 CH2CH2이고,X 1 , X 2 , Y 1 , Y 2 , Z 1 and Z 2 are each CH 2 or CH 2 CH 2 ,

R1, R3및 R4는 각각 수소; 또는 치환되거나 치환되지 않은 C1∼C10알킬이며,R 1 , R 3 and R 4 are each hydrogen; Or substituted or unsubstituted C 1 -C 10 alkyl,

R2는 C1∼C10히드록시알킬이고,R 2 is C 1 -C 10 hydroxyalkyl,

R*는 산에 민감한 보호기(acid labile protecting group)이며,R * is an acid labile protecting group,

p, q 및 r 은 각각 0∼2 중에서 선택되는 정수이고,p, q and r are each an integer selected from 0 to 2,

a : b : c : d 는 5∼90 mol% : 5∼90 mol% : 0∼90 mol% : 0∼90 mol%이다.a: b: c: d is 5 to 90 mol%: 5 to 90 mol%: 0 to 90 mol%: 0 to 90 mol%.

상기 산에 민감한 보호기란 산에 의해 탈리될 수 있는 그룹으로서, 포토레지스트 물질의 알칼리 현상액에 대한 용해 여부를 결정한다. 즉, 산에 민감한 보호기가 붙어있는 경우에는 포토레지스트 물질이 알칼리 현상액에 의해 용해되는 것이 억제되며, 노광에 의해 발생된 산에 의해 산에 민감한 보호기가 탈리되면 포토레지스트 물질이 현상액에 용해될 수 있게 된다. 이러한 산에 민감한 보호기는 상기와 같은 역할을 수행할 수 있는 것이면 무엇이든 가능하며, 그 예로는 US 5,212,043 (1993. 5. 18), WO 97/33198 (1997. 9. 12), WO 96/37526 (1996. 11. 28), EP 0 794 458 (1997. 9. 10), EP 0 789 278 (1997. 8. 13), US 5,750,680 (1998. 5. 12), GB 2,340,830 A (2000. 3. 1), US 6,051,678 (2000. 4. 18), GB 2,345,286 A (2000. 7. 5), US 6,132,926 (2000. 10. 17), US 6,143,463 (2000. 11. 7), US 6,150,069 (2000. 11. 21), US 6,180,316 B1 (2001. 1. 30), US 6,225,020 B1 (2001. 5. 1), US 6,235,448 B1 (2001. 5. 22) 및 US 6,235,447 B1 (2001. 5. 22) 등에 개시된 것을 포함하고, 바람직하게는t-부틸, 테트라히드로피란-2-일, 2-메틸 테트라히드로피란-2-일, 테트라히드로퓨란-2-일, 2-메틸 테트라히드로퓨란-2-일, 1-메톡시프로필, 1-메톡시-1-메틸에틸, 1-에톡시프로필, 1-에톡시-1-메틸에틸, 1-메톡시에틸, 1-에톡시에틸,t-부톡시에틸, 1-이소부톡시에틸 또는 2-아세틸멘트-1-일 등이 될 수 있다.The acid-sensitive protecting group is a group that can be released by the acid, and determines whether or not the photoresist material is dissolved in the alkaline developer. That is, when an acid sensitive protecting group is attached, the photoresist material is suppressed from being dissolved by the alkaline developer, and when the acid sensitive protecting group is released by the acid generated by exposure, the photoresist material may be dissolved in the developing solution. do. Such acid-sensitive protecting groups can be any one which can play such a role, for example US 5,212,043 (May 18, 1993), WO 97/33198 (September 12, 1997), WO 96/37526 (Nov. 28, 1996), EP 0 794 458 (September 10, 1997), EP 0 789 278 (August 13, 1997), US 5,750,680 (May 12, 1998), GB 2,340,830 A (2000. 3. 1), US 6,051,678 (April 18, 2000), GB 2,345,286 A (July 5, 2000), US 6,132,926 (October 17, 2000), US 6,143,463 (November 7, 2000), US 6,150,069 (2000.11 21), US 6,180,316 B1 (January 30, 2001), US 6,225,020 B1 (May 1, 2001), US 6,235,448 B1 (May 22, 2001) and US 6,235,447 B1 (May 22, 2001) and the like. T -butyl, tetrahydropyran-2-yl, 2-methyl tetrahydropyran-2-yl, tetrahydrofuran-2-yl, 2-methyl tetrahydrofuran-2-yl, 1- Methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methoxyethyl, 1-ethoxyethyl, t -butoxyethyl, 1- Isobutoxyethyl It may be a cement such as 2-acetyl-1-yl.

본 발명의 노광공정에서 사용되는 노광원은 VUV, ArF, KrF, EUV, E-빔, X-선 또는 이온빔 등이 있다.Exposure sources used in the exposure process of the present invention include VUV, ArF, KrF, EUV, E-beam, X-ray or ion beam.

본 발명의 방법을 이용하면, 포토레지스트 패턴의 식각 특성을 향상시킬 수있을 뿐만 아니라, CD 균일도 (uniformity)를 향상시킬 수 있다는 부수적인 효과도 얻을 수 있다.Using the method of the present invention, not only can the etching characteristics of the photoresist pattern be improved, but also the side effect of improving the CD uniformity can be obtained.

또한 본 발명에서는, 상기 포토레지스트 패턴 형성방법에 의하여 제조된 반도체 소자를 제공한다.In addition, the present invention provides a semiconductor device manufactured by the photoresist pattern forming method.

이하 본 발명을 실시예에 의하여 상세히 설명한다. 단 실시예는 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples. However, the examples are only to illustrate the invention and the present invention is not limited by the following examples.

실시예 1. Relacs 물질을 이용한 미세 패턴 형성Example 1 Fine Pattern Formation Using Relacs Material

하기 화학식 1a의 중합체를 이용하여 제조된 감광제를 옥사이드가 증착되어 있는 웨이퍼에 도포하고 110℃ 온도로 60초 동안 가열한 후, ArF용 노광장비로 노광하고, 140℃ 온도로 90초 동안 가열한 다음 현상하여 도 2와 같은 패턴을 얻었다 (CD : 107.7nm). 여기에 Relacs 물질을 도포하고 110℃ 온도로 90초 동안 가열한 후 다시 현상하여 도 3과 같은 패턴을 형성하였다 (CD : 122.0nm).The photosensitive agent prepared using the polymer of Formula 1a was applied to a wafer on which oxide was deposited, heated at 110 ° C. for 60 seconds, exposed with an ArF exposure equipment, and heated at 140 ° C. for 90 seconds. It developed and obtained the pattern like FIG. 2 (CD: 107.7nm). A Relacs material was applied thereto, heated at 110 ° C. for 90 seconds, and developed again to form a pattern as illustrated in FIG. 3 (CD: 122.0 nm).

이렇게 형성된 패턴을 고 선택비의 식각 장비로 식각하여 하기 도 4와 같이 옥사이드 식각이 가능한 패턴을 얻을 수 있었다.The pattern thus formed was etched with a high selectivity etching equipment to obtain an oxide etchable pattern as shown in FIG. 4.

도 2의 CD는 107.7nm 이고 도 3의 CD는 122.0nm 이므로, 이와 같은 결과를 볼 때 감광제와 Relacs 물질간에 14.3nm 만큼 가교 반응이 일어난 것을 확인할 수 있었다.Since the CD of FIG. 2 is 107.7 nm and the CD of FIG. 3 is 122.0 nm, it was confirmed that the crosslinking reaction occurred by 14.3 nm between the photosensitive agent and the Relacs material.

[화학식 1a][Formula 1a]

상기 식에서 a : b : c 는 1.0 mol% : 0.85 mol% : 0.15 mol% 이다.Wherein a: b: c is 1.0 mol%: 0.85 mol%: 0.15 mol%.

실시예 2. Relacs 물질을 이용한 CD 균일도 개선Example 2 CD Uniformity Improvement Using Relacs Material

상기 실시예 1에서 Relacs 물질을 도포한 후 가열하는 온도를 각각 110℃, 150℃ 및 200℃로 실험한 결과 온도를 증가시킬수록 하기 표 1과 같이 CD 균일도가 향상되는 결과를 얻을 수 있었다.After applying the relacs material in Example 1, the heating temperature was tested at 110 ° C, 150 ° C, and 200 ° C, respectively, and as a result, CD uniformity was improved as shown in Table 1 below.

[표 1]TABLE 1

Relacs 가열 온도Relacs heating temperature CD 범위(균일도)CD range (uniformity) Relacs 물질 사용 전Before using Relacs substance 15.6nm15.6 nm Relacs 물질사용가열온도 : 110℃Heating Temperature of Relacs Material: 110 ℃ 12.3nm12.3 nm Relacs 물질사용가열온도 : 150℃Heating Temperature of Relacs Material: 150 ℃ 11.4nm11.4 nm Relacs 물질사용가열온도 : 200℃Heating Temperature of Relacs Material: 200 ℃ 7.9nm7.9 nm

상기 CD 범위 (range)는 웨이퍼 내에서 CD 균일도를 나타내는 척도로서 값이 제일 큰 CD와 제일 작은 CD와의 차이를 나타내므로 값이 작을수록 좋은 것이다.The CD range is a measure of CD uniformity in the wafer, and the smaller the value is, the better is the difference between the largest CD and the smallest CD.

이상에서 살펴본 바와 같이, 본 발명의 패턴 형성방법은 기존의 방법에 의해형성된 포토레지스트 패턴에 Relacs 물질을 도포하고 가열하여, 포토레지스트 패턴의 가장자리에서 가교가 일어나게 함으로써 포토레지스트 막의 식각 내성을 증가시켜 소자의 고집적화를 향상시키는 결과를 가져온다. 또한 본 발명에서는 부수적인 효과로서 CD 균일도를 향상시키는 결과도 얻을 수 있다.As described above, in the pattern forming method of the present invention, by applying and heating a relacs material on a photoresist pattern formed by a conventional method, crosslinking occurs at the edge of the photoresist pattern, thereby increasing the etching resistance of the photoresist film. This results in improved high integration. In addition, in the present invention, the result of improving the CD uniformity can be obtained as a side effect.

Claims (6)

(a) 피식각층 상부에 포토레지스트 막을 형성하는 단계;(a) forming a photoresist film on the etched layer; (b) 상기 포토레지스트 막을 선택적으로 노광 및 현상하여 1차 포토레지스트 패턴을 형성하는 단계;(b) selectively exposing and developing the photoresist film to form a primary photoresist pattern; (c) 상기 포토레지스트 패턴에 Relacs 물질을 도포하여 가열하는 단계; 및(c) applying and heating a Relacs material on the photoresist pattern; And (d) 상기 (c) 단계의 결과물을 현상하여 2차 포토레지스트 패턴을 형성하는 단계를 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법.(d) developing the resultant of step (c) to form a secondary photoresist pattern. 제 1 항에 있어서,The method of claim 1, 상기 포토레지스트 막에 사용되는 포토레지스트 중합체는 하기 화학식 1의 중합반복단위를 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법.The photoresist polymer used in the photoresist film is a photoresist pattern forming method characterized in that it comprises a polymerization repeating unit of the formula (1). [화학식 1][Formula 1] 상기 식에서,Where X1, X2, Y1, Y2, Z1및 Z2는 각각 CH2또는 CH2CH2이고,X 1 , X 2 , Y 1 , Y 2 , Z 1 and Z 2 are each CH 2 or CH 2 CH 2 , R1, R3및 R4는 각각 수소; 또는 치환되거나 치환되지 않은 C1∼C10알킬이며,R 1 , R 3 and R 4 are each hydrogen; Or substituted or unsubstituted C 1 -C 10 alkyl, R2는 C1∼C10히드록시알킬이고,R 2 is C 1 -C 10 hydroxyalkyl, R*는 산에 민감한 보호기(acid labile protecting group)이며,R * is an acid labile protecting group, p, q 및 r 은 각각 0∼2 중에서 선택되는 정수이고,p, q and r are each an integer selected from 0 to 2, a : b : c : d 는 5∼90 mol% : 5∼90 mol% : 0∼90 mol% : 0∼90 mol%이다.a: b: c: d is 5 to 90 mol%: 5 to 90 mol%: 0 to 90 mol%: 0 to 90 mol%. 제 1 항에 있어서,The method of claim 1, 상기 (c) 단계의 가열 온도는 90∼150℃인 것을 특징으로 하는 포토레지스트 패턴 형성방법.The heating temperature of the step (c) is a photoresist pattern forming method, characterized in that 90 ~ 150 ℃. 제 1 항에 있어서,The method of claim 1, 상기 (b) 단계의 노광전에 소프트 베이크 공정을 수행하고, 노광후에 포스트 베이크 공정을 수행하는 단계를 더 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법.And performing a soft bake process before the exposure in step (b) and a post bake process after the exposure. 제 1 항에 있어서,The method of claim 1, 상기 노광공정의 노광원은 VUV, ArF, KrF, EUV, E-빔, X-선 및 이온빔으로 이루어진 군으로부터 선택된 것을 특징으로 하는 포토레지스트 패턴 형성방법.The exposure source of the exposure process is a photoresist pattern forming method, characterized in that selected from the group consisting of VUV, ArF, KrF, EUV, E-beam, X-rays and ion beams. 제 1 항 기재의 방법에 의하여 제조된 반도체 소자.A semiconductor device manufactured by the method of claim 1.
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