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
step
material
relacs
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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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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273Making 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
    • H01L21/0274Photolithographic processes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16Coating processes; Apparatus therefor
    • G03F7/168Finishing the coated layer, e.g. drying, baking, soaking
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/38Treatment 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} Using a material Relacs method of forming the etching resistant improved photoresist pattern {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 invention Relacs (resist enhancement lithography assisted by chemical shrink) by using the materials relates to a method of improving the etching characteristics of photoresist, and more particularly, to heating and re-development after applying the Relacs material on preformed photoresist pattern by to a method of forming the etching resistant photoresist pattern is improved.

100nm 이하의 초미세 회로를 사용한 4G DRAM 또는 16G DRAM 제조에 있어서, 패턴이 미세화 됨에 따라 포토레지스트의 두께가 얇아져야 패턴 형성이 가능하다. In the production 4G 16G DRAM or a DRAM with an ultrafine circuit of 100nm or less, the thickness of the photoresist should be thinned as the pattern miniaturization is possible to pattern formation. 포토레지스트 패턴은 하부막 식각 공정시에 일정한 두께를 유지해야 하는데 패턴의 두께가 얇아지면 이것이 곤란해지므로, 포토레지스트가 가져야 할 필수조건은 식각 내성이다. The photoresist pattern is to be maintained a constant thickness at the time of the lower film by the etching process because the thickness of the thinner pattern this is difficult, a requirement to have a photoresist is etching resistant. 그러나 이 식각 내성의 극복은 사실상 매우 곤란하다. However, overcoming of the etching resistance is practically very difficult. 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. That is, inde In a highly integrated device using an etching selection ratio high photosensitive agent is essential, if the photosensitive material for ArF light sources that are currently commercially available is low, select etch for oxide film ratio to form a pattern by the conventional method, as can be seen in Figure 5 there arises a problem that the 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. The present inventors have completed the present invention that it is the taking out of the ohdeon effort to improve the etching characteristics of the photoresist, when applying a material Relacs the formed photoresist pattern can be etched oxide.

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

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

도 2는 실시예 1에서, Relacs 물질을 도포하기 전에 형성된 패턴 사진. In Figure 2 the first embodiment, picture pattern formed prior to the application of the Relacs material.

도 3은 실시예 1에서, Relacs 물질을 도포하여 가열한 후 현상하여 형성된 패턴 사진. 3 is then in the first embodiment, heat is applied the material Relacs pattern formed by photo development.

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

도 5는 종래의 방법으로 형성된 포토레지스트 패턴으로 옥사이드를 식각한 결과를 나타낸 사진. 5 is a photograph showing a result of etching the oxide with a photoresist pattern formed by the 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. By heating after application of the material to Relacs photoresist pattern already formed in the present invention, in order to attain the object and back phenomenon provides a method of forming the etching resistant photoresist pattern is improved.

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). Relacs (resist enhancement lithography assisted by chemical shrink) material refers to a material that is commercialized with a license from Clariant (Clariant) used, is mainly used in the step of reducing the contact hole size (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. In the present invention, using such a material Relacs improves the etching characteristics of photoresist patterns and characters.

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, According to the present invention to provide a method of using the material Relacs improve the etching characteristics of photoresist, specifically,

(a) 피식각층 상부에 포토레지스트 막을 형성하는 단계; (A) etching to form the respective layers in the upper photoresist film;

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

(c) 상기 포토레지스트 패턴에 Relacs 물질을 도포하여 가열하는 단계; (C) heating the coated 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) providing a photoresist pattern forming process comprising the step of forming a second pattern having a cross-linking of the Relacs material on the edge of the step (c) the first photo-resist pattern by developing the product of.

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. Wherein (a) and step (b) [(a) and (b) a reference to Fig. 1, the soft-baking process prior to the exposure of the step (b) a process of forming a photoresist pattern by the conventional pattern formation method to perform, and may further comprise the step of performing a post-baking 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. The (c) and (d) is the step which is new according to the present invention, it is Relacs material can be applied on the pattern formed in (b) Since the water solubility. 도포가 끝난 후 가열하면 감광제의 가장자리에 남아있는 산이 Relacs 물질쪽으로 확산되어 Relacs 물질과 감광제 사이에서 일부가 가교반응을 일으킨다 [도 1의 (c) 참조]. If heating is applied after the end of the acid remaining in the edge of the photosensitive material is diffused toward Relacs material causes some cross-linking reaction occurs between the material and the photosensitive material Relacs [in Fig. 1 (c) reference. 이때 산이 확산된 거리만큼 포토레지스트 수지와 Relacs 물질간의 가교반응이 일어나는데, 온도에 따라 산의 확산 거리가 다르므로 이에 따라 가교되는 면적이 결정되게 된다. The acid ileonaneunde the crosslinking reaction between the diffusion distance of the photoresist resin and Relacs material, since the diffusion distance of the acid depends on the temperature whereby the area to be cross-linked are to be determined. 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]. Phenomenon during, Micah water-soluble substance of Relacs material with a training state becomes not dissolved, the cross-linked site has been left without being dissolved in the primary pattern than the cross-linked sites as CD is larger the second pattern formation formed in the step (b) will be Fig. (d) of the reference 1]. 한편, 상기 (c) 단계의 가열 온도는 90∼150℃인 것이 바람직하다. On the other hand, the heating temperature of 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. Photosensitive agent used in the pattern forming method of the present invention, i.e., a photoresist composition which would be one, in particular the base resin in the photoresist composition containing a photo-acid generator or a thermal acid generating agent is preferable, and a photoresist composition is especially cycloolefins backbone (back bone) as having a structure, when a predetermined functional group (functional group), for example, cycloalkyl cycloalkyl olefin comonomer having sensitive protecting group and the carboxylic acid, and the like of the function to the acid which acts group dissolution inhibiting to the addition polymerization preferably includes a repeating unit a ring (ring) structure of an olefin backbone, which is held in the main chain not been broken, and more preferably containing cycloolefins comonomer having hydroxyalkyl functionality for substrate adhesion and sensitivity adjustment is recommended.

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, in order to improve the adhesion to the substrate 2-hydroxy-ethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate or 2-hydroxy-ethyl bicyclo [2.2.2] oct -5 -en-2-carboxylate to the example it is desirable, and for example comprising the comonomers may include a base resin containing a polymerization repeating unit of formula (1).

[화학식 1] Formula 1

상기 식에서, Wherein

X 1 , X 2 , Y 1 , Y 2 , Z 1 및 Z 2 는 각각 CH 2 또는 CH 2 CH 2 이고, X 1, X 2, Y 1 , Y 2, Z 1 and Z 2 are each CH 2 or CH 2 CH 2,

R 1 , R 3 및 R 4 는 각각 수소; R 1, R 3 and R 4 are each hydrogen; 또는 치환되거나 치환되지 않은 C 1 ∼C 10 알킬이며, Or an optionally substituted C 1 ~C 10 alkyl,

R 2 는 C 1 ∼C 10 히드록시알킬이고, R 2 is a C 1 ~C 10 hydroxyalkyl,

R*는 산에 민감한 보호기(acid labile protecting group)이며, R * is a sensitive protecting groups (acid labile protecting group) in the acid,

p, q 및 r 은 각각 0∼2 중에서 선택되는 정수이고, And p, q and r is an integer selected from 0 to 2, respectively,

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

상기 산에 민감한 보호기란 산에 의해 탈리될 수 있는 그룹으로서, 포토레지스트 물질의 알칼리 현상액에 대한 용해 여부를 결정한다. As a group which may be eliminated sensitive protecting groups on the acid is an acid, it is determined whether or not dissolved in an alkali developing solution of the photoresist material. 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. That is, if the acid is attached sensitive protecting groups include, are suppressed from the photoresist material which is dissolved by the alkaline developer, when by the acid generated by exposure, elimination-sensitive protecting group on the acid allow the photoresist material may be dissolved in the developer do. 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, 바람직하게는 t -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 Sensitive protecting group on the acid shall be anything as long as it can act as described above. Examples are 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), that disclosed in US 6,180,316 B1 (2001. 1. 30), US 6,225,020 B1 (2001. 5. 1), US 6,235,448 B1 (2001. 5. 22), and US 6,235,447 B1 (2001. 5. 22) includes, preferably, t - butyl, tetrahydropyran-2-yl, 2-methyl-tetrahydropyran-2-yl, tetrahydrofuran-2-yl, 2-methyl-tetrahydrofuran-2-yl, 1 methoxypropyl, 1-methoxy-1-methyl-ethyl, ethoxy, propyl, 1-1-ethoxy-1-methylethyl, 1-methoxyethyl, 1-ethoxy ethyl, t - butoxy-ethyl, 1- isobutoxy-ethyl 는 2-아세틸멘트-1-일 등이 될 수 있다. 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. An exposure light source used in the exposure process of the present invention to provide a VUV, ArF, KrF, EUV, E- beam, such as X- ray, or ion beams.

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

또한 본 발명에서는, 상기 포토레지스트 패턴 형성방법에 의하여 제조된 반도체 소자를 제공한다. In the present invention, there is provided a semiconductor device fabricated by the photoresist pattern forming method.

이하 본 발명을 실시예에 의하여 상세히 설명한다. It will be described in detail below by the present invention in embodiments. 단 실시예는 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다. However embodiments are intended as but is not limited by the embodiment to which the present invention illustrating the invention.

실시예 1. Relacs 물질을 이용한 미세 패턴 형성 Example 1 Using a fine pattern forming material Relacs

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). To applying a photosensitive material produced using a polymer of the formula (1a) on the wafer is oxide is deposited and exposed to the post-heated for 60 seconds at a temperature 110 ℃, ArF exposure equipment, and heated for 90 seconds at a temperature 140 ℃ then It was obtained by developing a pattern, such as 2 (CD: 107.7nm). 여기에 Relacs 물질을 도포하고 110℃ 온도로 90초 동안 가열한 후 다시 현상하여 도 3과 같은 패턴을 형성하였다 (CD : 122.0nm). This was applied to a Relacs material to form a pattern such as Figure 3 to a re-heating after development for 90 seconds at a temperature 110 ℃ (CD: 122.0nm).

이렇게 형성된 패턴을 고 선택비의 식각 장비로 식각하여 하기 도 4와 같이 옥사이드 식각이 가능한 패턴을 얻을 수 있었다. To do this, the pattern formed by said etching in the etching equipment of the selectivity could be obtained capable of oxide etch pattern as shown in FIG.

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. Because the CD of Figure 2 is 107.7nm and 122.0nm CD of Figure 3, it was confirmed that the crosslinking takes place by a reaction between this 14.3nm when viewing the same photosensitive agent as a result Relacs material.

[화학식 1a] [Chemical 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%: a 0.15 mol%.

실시예 2. Relacs 물질을 이용한 CD 균일도 개선 Example 2. The improved CD uniformity using a material Relacs

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. To more increase the above-described embodiment 1, the result of the experiment the temperature to the temperature at which heat was applied to the material Relacs 110 ℃, 150 ℃ and 200 ℃ respectively were obtained the results that the improved CD uniformity as shown in Table 1.

[표 1] TABLE 1

Relacs 가열 온도 Relacs heating temperature CD 범위(균일도) CD range (uniformity)
Relacs 물질 사용 전 Relacs materials before use 15.6nm 15.6nm
Relacs 물질사용가열온도 : 110℃ Relacs material using a heating temperature: 110 ℃ 12.3nm 12.3nm
Relacs 물질사용가열온도 : 150℃ Relacs material using a heating temperature: 150 ℃ 11.4nm 11.4nm
Relacs 물질사용가열온도 : 200℃ Relacs material using a heating temperature: 200 ℃ 7.9nm 7.9nm

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 (range) is a smaller value exhibits a great difference between the largest and the smallest CD CD the value as a measure of the CD uniformity within a wafer.

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. As described above, the pattern forming method of the present invention by coating and heating the Relacs material on the photoresist pattern formed by the conventional method, since the cross-linking occurs at the edges of the photoresist pattern by increasing the photoresist film etch resistance element the results in improving the degree of integration. 또한 본 발명에서는 부수적인 효과로서 CD 균일도를 향상시키는 결과도 얻을 수 있다. In addition, results can be obtained to improve CD uniformity as a side effect in the present invention.

Claims (6)

  1. (a) 피식각층 상부에 포토레지스트 막을 형성하는 단계; (A) etching to form the respective layers in the upper photoresist film;
    (b) 상기 포토레지스트 막을 선택적으로 노광 및 현상하여 1차 포토레지스트 패턴을 형성하는 단계; (B) a step of selectively exposing and developing to form a first photoresist pattern the photoresist film;
    (c) 상기 포토레지스트 패턴에 Relacs 물질을 도포하여 가열하는 단계; (C) heating the coated 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) a photoresist pattern forming method comprising the step of forming a second photoresist pattern by developing the product of step (c).
  2. 제 1 항에 있어서, According to claim 1,
    상기 포토레지스트 막에 사용되는 포토레지스트 중합체는 하기 화학식 1의 중합반복단위를 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법. The photoresist polymer to the photoresist pattern-forming method comprising a polymerization repeating unit of formula (1) used in the photoresist film.
    [화학식 1] Formula 1
    상기 식에서, Wherein
    X 1 , X 2 , Y 1 , Y 2 , Z 1 및 Z 2 는 각각 CH 2 또는 CH 2 CH 2 이고, X 1, X 2, Y 1 , Y 2, Z 1 and Z 2 are each CH 2 or CH 2 CH 2,
    R 1 , R 3 및 R 4 는 각각 수소; R 1, R 3 and R 4 are each hydrogen; 또는 치환되거나 치환되지 않은 C 1 ∼C 10 알킬이며, Or an optionally substituted C 1 ~C 10 alkyl,
    R 2 는 C 1 ∼C 10 히드록시알킬이고, R 2 is a C 1 ~C 10 hydroxyalkyl,
    R*는 산에 민감한 보호기(acid labile protecting group)이며, R * is a sensitive protecting groups (acid labile protecting group) in the acid,
    p, q 및 r 은 각각 0∼2 중에서 선택되는 정수이고, And p, q and r is an integer selected from 0 to 2, respectively,
    a : b : c : d 는 5∼90 mol% : 5∼90 mol% : 0∼90 mol% : 0∼90 mol%이다. a: b: c: d is 5~90 ​​mol%: 5~90 ​​mol%: 0~90 mol%: is 0~90 mol%.
  3. 제 1 항에 있어서, According to claim 1,
    상기 (c) 단계의 가열 온도는 90∼150℃인 것을 특징으로 하는 포토레지스트 패턴 형성방법. (C) the temperature of the heating step is forming a photoresist pattern, characterized in that 90~150 ℃.
  4. 제 1 항에 있어서, According to claim 1,
    상기 (b) 단계의 노광전에 소프트 베이크 공정을 수행하고, 노광후에 포스트 베이크 공정을 수행하는 단계를 더 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법. Perform a soft-bake step prior to the exposure of the step (b), and a photoresist pattern forming method according to claim 1, further comprising the step of performing a post-baking process after the exposure.
  5. 제 1 항에 있어서, According to claim 1,
    상기 노광공정의 노광원은 VUV, ArF, KrF, EUV, E-빔, X-선 및 이온빔으로 이루어진 군으로부터 선택된 것을 특징으로 하는 포토레지스트 패턴 형성방법. An exposure light source is VUV, ArF, KrF, EUV, E- beam, X- ray and a method of forming a photoresist pattern, characterized in that it is selected from the group consisting of an ion beam in the exposure process.
  6. 제 1 항 기재의 방법에 의하여 제조된 반도체 소자. The semiconductor device produced by the method of 1, wherein the substrate.
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