KR20010057590A - Edge bead remover - Google Patents

Edge bead remover Download PDF

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Publication number
KR20010057590A
KR20010057590A KR1020000082464A KR20000082464A KR20010057590A KR 20010057590 A KR20010057590 A KR 20010057590A KR 1020000082464 A KR1020000082464 A KR 1020000082464A KR 20000082464 A KR20000082464 A KR 20000082464A KR 20010057590 A KR20010057590 A KR 20010057590A
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KR
South Korea
Prior art keywords
acetate
edge bead
ether
bead remover
resist
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KR1020000082464A
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Korean (ko)
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KR100733650B1 (en
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노가미켄키
아오야마데츠오
Original Assignee
오오히라 아키라
미츠비시 가스 가가쿠 가부시키가이샤
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Priority claimed from JP37283199A external-priority patent/JP2001188358A/en
Priority claimed from JP37283299A external-priority patent/JP2001188359A/en
Priority claimed from JP37283399A external-priority patent/JP2001188360A/en
Application filed by 오오히라 아키라, 미츠비시 가스 가가쿠 가부시키가이샤 filed Critical 오오히라 아키라
Publication of KR20010057590A publication Critical patent/KR20010057590A/en
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Publication of KR100733650B1 publication Critical patent/KR100733650B1/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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

PURPOSE: Provided is an edge bead remover having an excellent resist dissolution rate, low toxicity and very high safety, excellent also in environmental preservation giving out little unpleasant odor, having a relatively high boiling point and good operability, forming no residue or deposit and capable of efficiently producing a high-grade substrate for the production of electronic parts. CONSTITUTION: The edge bead remover is comprised of a mixture of methyl alpha-hydroxyisobutyrate and a compound of the following formula(I): wherein R is hydrogen or acetyl radical, R1 is hydrogen or methyl radical, R2 is alkyl having 1-4 carbons, and n is an integer of 0-3, provided that n is an integer of 1-3, when R is hydrogen. The ratio by weight of methyl alpha-hydroxyisobutyrate to the compound of formula(I) is 9:1-1:9. The compound is preferably glycol monoalkylether. The remover is used to remove an unnecessary resist composition attached to substrate.

Description

엣지비드 리무버{EDGE BEAD REMOVER}EDGE BEAD REMOVER}

본 발명은 신규의 엣지비드 리무버(edge bead remover)에 관계하며, 이 엣지비드 리무버를 사용해서 레지스트(resist) 도포시 혹은 도포후의 전자부품용 기판으로부터 불필요한 레지스트분을 세정제거하는 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel edge bead remover and relates to a method for cleaning and removing unnecessary resist powder from an electronic component substrate during or after applying a resist using the edge bead remover.

레지스트등의 도포에는 스핀도포, 롤도포, 리버스롤 도포, 유연도포, 독터도포, 딥도포, 랜드도포등의 각종의 방법이 채용되고 있고, 예를들면 집적회로소자의 제조에 있어서는, 레지스트도포법으로서 스핀도포가 주로 사용되고 있다.Various coating methods, such as spin coating, roll coating, reverse roll coating, flexible coating, doctor coating, dip coating, and land coating, are employed for coating the resist. For example, in the manufacture of integrated circuit devices, the resist coating method is employed. Spin coating is mainly used.

스핀도포법에서는 기판상에 레지스트용액이 적하되고, 이 적하된 레지스트용액은 기판의 회전에 의해 기판외부 원주방향으로 퍼져나가고, 과잉의 레지스트용액은 기판 외부원주로부터 비산제거되고, 기판중심부는 소망하는 막의 두께를 갖는 레지스트막이 형성된다.In the spin coating method, a resist solution is dropped on a substrate, and the dropped resist solution is spread out in the circumferential direction outside the substrate by the rotation of the substrate, the excess resist solution is scattered and removed from the outer circumference of the substrate, and the substrate center portion is desired. A resist film having a thickness of the film is formed.

이때 레지스트용액의 일부가 기판의 배면에까지 도달하거나 혹은 기판의 외부 원주둘레에는 레지스트용액이 다른 부분보다 두껍게 남는 소위 비드의 형성이 이루어지는 결점이 있다.At this time, there is a drawback that a part of the resist solution reaches the rear surface of the substrate, or a so-called bead is formed on the outer circumference of the substrate so that the resist solution remains thicker than other portions.

이와같은 레지스트는 다음공정의 열처리에 의해 무르게되어 기판의 반송중에적은 비늘조각상으로 박리되고, 이것이 장치내의 먼지발생의 원인이 되거나 기판상의 레지스트 표면에 부착하여 고품질의 반도체소자를 제조하는데 있어서, 큰문제로되어있다.Such a resist is softened by heat treatment in the next step and peeled off in a small scale during the conveyance of the substrate, which causes dust in the apparatus or adheres to the resist surface on the substrate to produce a high quality semiconductor device. Is supposed to.

이 때문에 기판측면 주변부 혹은 이면으로부터 불필요한 레지스트를 제거하거나 비드의 제거를 행할 필요가 있다.For this reason, it is necessary to remove unnecessary resist or remove beads from the periphery or the back side of the substrate side.

또 스핀도포법 이외의 도포법에 있어서도 불필요한 부분에 레지스트가 부착되는 일이 있는 것은 스핀도포법 경우와 같은 모양이다.Also, in the coating method other than the spin coating method, the resist may adhere to unnecessary portions in the same manner as in the spin coating method.

이 불필요한 레지스트의 제거에 사용되는 용제가 「엣지비드 리무버」이다.The solvent used for removing this unnecessary resist is an "edge bead remover".

미국특허 5,814,433에 기재되어 있는 바와 같이, 엣지비드 리무버는 패턴노출전의 레지스트 제거에 사용되고, 엣칭 종료후 불필요하게된 레지스트패턴을 기판으로부터 제거하기 위한 레지스트 박리제와는 사용시기만이 아니라, 요구되는 특성에 있어서도 현저히 다르다.As described in US Pat. No. 5,814,433, the edge bead remover is used for removing resist before pattern exposure, and it is not only used at the time of use but also with a resist stripper for removing a resist pattern unnecessary from the substrate after the end of etching. Significantly different.

종래에 엣지비드 리무버에 사용되고 있는 용제로서 예를들면 일본국 특개소 63-69563호 공보에서는 1-메틸-2-피롤리돈, 아세톤, 크실렌의 사용이 기술되고, 또하나의 예로서 일본국 특개평 7-146562호 공보에서는, 레지스트제거용 세정용제로서 에틸렌글리콜모노알킬에테르, 에틸렌글리콜 모노알킬에테르 아세테이트, 프로필렌글리콜 모노알킬에테르, 프로필렌글리콜 모노알킬아세테이트 등의 에테르나 에테르아세테이트류, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥사논 등의 케톤류, 락트산메틸, 락트산에틸, 아세트산메틸, 아세트산에틸, 아세트산부틸, 3-메톡시프로피온산메틸, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸 등의 에스테르류나 알콕시카르복실산 에스테르류 혹은 이들의 혼합물 등의 사용이 종래예를 포함해서 기술되어있다.For example, Japanese Unexamined Patent Application Publication No. 63-69563 discloses the use of 1-methyl-2-pyrrolidone, acetone, and xylene as a solvent used in edge bead removers. JP-A 7-146562 discloses ethers and ether acetates such as ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol monoalkyl acetate, acetone, and methyl ethyl as cleaning solvents for resist removal. Ketones such as ketones, methyl isobutyl ketones and cyclohexanone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate The use of esters, alkoxycarboxylic acid esters or mixtures thereof is described, including conventional examples. All.

그러나 종래의 세정제는 어떤 것은 레지스트에 대한 용해능력이 충분하지 않고, 세정시에 잔류물이나 석출물이 생기기 쉽고, 충분한 세정을 행하기 위해서는 시간이 걸리거나 다량의 세정제가 필요하게 된다.However, some conventional cleaning agents do not have sufficient dissolving ability to resist, and residues or precipitates are liable to be generated at the time of cleaning, and it takes time or a large amount of cleaning agent to perform sufficient cleaning.

또 증발속도가 느린 것은 건조성이 나빠 사용하는데 불리하게 되고 역으로 대부분의 케톤, 에스테르는 증기압이 높아져 작업성이 나빠진다.In addition, the slow evaporation rate is disadvantageous in use due to poor drying properties, and conversely, most ketones and esters have high vapor pressure and thus poor workability.

다시또 용해력이 높은 에틸렌글리콜계를 위시하여 각 용제에는 많거나 적거나 독성을 가짐과 동시에 불쾌한 냄새를 발생시키는 것이 많고, 우수한 용해성과, 인체에 대한 보다 우수한 안전성을 동시에 만족시키는 세정제가 요망되고 있다.In addition, ethylene glycol-based solvents, which are highly soluble in solvents, have many, few, or toxic solvents, and have an unpleasant odor, and a cleaner that satisfies both excellent solubility and better safety for the human body is desired. .

이것은 집적회로소자의 제조에 한정되지않고, 컬러필터, 액정표시소자 등의 제조에 있어서도 같은 모양이다.This is not limited to the manufacture of the integrated circuit elements, but also in the manufacture of color filters, liquid crystal display elements and the like.

본 발명은 상기한 결점을 갖지않는 소량의 사용량으로, 또한 단시간의 세정시간으로 불필요한 레지스트를 충분히 제거할 수 있는, 고용해성을 가짐과 동시에 인체에 대해서 안전성이 높고, 작업성도 우수한 엣지비드 리무버를 제공하는 것을 목적으로 한다.The present invention provides an edge bead remover having high solubility and high workability and excellent workability, capable of sufficiently removing unnecessary resists in a small amount of use that does not have the above-mentioned drawbacks and in a short cleaning time. It aims to do it.

본 발명자 등은 예의 연구한 결과, α-히드록시이소부티르산메틸과, 하기 일반식 (Ⅰ) :MEANS TO SOLVE THE PROBLEM As a result of earnestly research, the present inventors have shown that (alpha) -hydroxyisobutyrate and general formula (I):

R1 R 1

｜｜

RO-(CHCH2O)n-R2(Ⅰ)RO- (CHCH 2 O) n -R 2 (I)

(R는 수소 또는 아세틸기, R1은 수소 또는 메틸기, R2는 탄소수 1∼4의 알킬기, n은 0∼3의 정수를 나타낸다. 단 R이 수소를 나타낼 때 n은 1∼3의 정수를 나타낸다)로 표시되는 화합물과의 균질용제를 엣지비드 리무버로서 사용하므로서, 소량의 사용량으로 또한 단시간의 세정시간으로, 불필요한 레지스트를 충분히 제거할수 있는 높은 용해성을 갖고, 인체에 대해서 안전성이 크고 유기용제에 있을 수 있는 불쾌한 냄새가 극히 적고, 작업성이 우수한 엣지비드 리무버로 되는 것을 발견해서 본 발명을 달성하게 된 것이다.(R is hydrogen or an acetyl group, R 1 is hydrogen or methyl group, R 2 is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 3. However, when R represents hydrogen, n is an integer of 1 to 3 By using a homogeneous solvent with the compound represented as an edge bead remover, it has a high solubility that can remove unnecessary resist sufficiently in a small amount of use and a short cleaning time, and is safe to the human body, The present invention has been accomplished by discovering an edge bead remover having extremely low unpleasant odor and excellent workability.

즉 본발명은 α-히드록시이소부티르산메틸과, 하기식 (Ⅰ) :Namely, the present invention provides α-hydroxyisobutyrate methyl and the following formula (I):

R1 R 1

｜｜

RO-(CHCH2O)n-R2(Ⅰ)RO- (CHCH 2 O) n -R 2 (I)

(R는 수소 또는 아세틸기, R1은 수소 또는 메틸기, R2는 탄소수 1∼4의 알킬기, n은 0∼3의 정수를 나타낸다. 단 R이 수소를 나타낼 때 n은 1∼3의 정수를 나타낸다)로 표시되는 화합물을 함유하는 것을 특징으로 하는 엣지비드 리무버이며, 이 엣지비드 리무버를 사용하므로서, 인체에 대한 안전성이 높고, 유기용제에 있을 수 있는 불쾌한 냄새를 크게 감소하면서, 레지스트 도포시 혹은 도포후의 전자부품용 기판으로부터 불필요한 레지스트분을 소량의 용제사용량으로 단시간에 제거하는 방법이다.(R is hydrogen or an acetyl group, R 1 is hydrogen or methyl group, R 2 is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 3. However, when R represents hydrogen, n is an integer of 1 to 3 It is an edge bead remover, characterized in that it contains a compound represented by the above formula, and by using this edge bead remover, it is highly safe for the human body and greatly reduces the unpleasant odor that may be present in an organic solvent, It is a method of removing unnecessary resist powder in a short amount of time using a small amount of solvent from the electronic component substrate after coating.

상기한 일반식(Ⅰ)의 화합물은 R이 수소의 경우에는 글리콜모노알킬에테르를, R이 아세틸기이며, n이 1∼3의 정수인경우에는 글리콜모노알킬에테르아세테이트를, R이 아세틸기이며, n이 영(0)인 경우에는 아세트산에스테르를 나타낸다.The compound of the general formula (I) is a glycol monoalkyl ether when R is hydrogen, R is an acetyl group, a glycol monoalkyl ether acetate when n is an integer of 1 to 3, R is an acetyl group, When n is zero, an acetate ester is shown.

상기한 일반식(Ⅰ)로 표시되는 글리콜모노알킬에테르로서는 예를들면, 디에틸렌글리콜 모노메틸에테르, 디에틸렌글리콜 모노에틸에테르, 디에틸렌글리콜 모노부틸에테르, 트리에틸렌글리콜 모노메틸에테르, 트리에틸렌글리콜 모노에틸에테르, 트리에틸렌글리콜 모노부틸에테르, 프로필렌글리콜 모노메틸에테르, 프로필렌글리콜 모노에틸에테르, 프로필렌글리콜 모노부틸에테르, 디프로필렌글리콜 모노메틸에테르, 디프로필렌글리콜 모노에틸에테르, 디프로필렌글리콜 모노부틸에테르 등을 들 수 있고, 특히 바람직하게는 프로필렌글리콜 모노메틸에테르이다.As glycol monoalkyl ether represented by said general formula (I), for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, etc. These are mentioned, Especially preferably, it is propylene glycol monomethyl ether.

상기한 일반식(Ⅰ)로 표시되는 글리콜모노알킬에테르 아세테이트로서는 예를들면, 디에틸렌글리콜 모노메틸에테르아세테이트, 디에틸렌글리콜 모노에틸에테르 아세테이트, 디에틸렌글리콜 모노부틸에테르아세테이트, 프로필렌글리콜 모노메틸에테르아세테이트, 프로필렌글리콜 모노에틸에테르아세테이트, 프로필렌글리콜 모노부틸에테르아세테이트 등을 들 수 있고, 특히 바람직하게는 프로필렌글리콜 모노메틸에테르아세테이트이다.As glycol monoalkyl ether acetate represented by said general formula (I), for example, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate And propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and the like, and particularly preferably propylene glycol monomethyl ether acetate.

상기한 일반식 (Ⅰ)로 표시되는 아세트산에스테르로서는 예를들면, 아세트산메틸, 아세트산에틸, 아세트산부틸 등을 들수가 있고, 특히 바람직하게는 아세트산부틸이다.As acetate acetate represented by said general formula (I), methyl acetate, ethyl acetate, butyl acetate, etc. are mentioned, for example, Especially preferably, it is butyl acetate.

상기한 글리콜모노알킬에테르, 글리콜모노알킬에테르 아세테이트 및 아세트산에스테르는 단독으로 사용해도 되고 또 2종이상을 조합해서 사용할수도 있다.Said glycol monoalkyl ether, glycol monoalkyl ether acetate, and acetate ester may be used individually, or may be used in combination of 2 or more type.

본발명의 엣지비드 리무버는 α-히드록시이소부티르산메틸, 일반식(Ⅰ)로 표시되는 화합물 및 임의로 사용되는 레지스트 제거상 허용되는 첨가물과의 균질혼합물이 얻어지는 것이라면 어떠한 방법으로 제조해도 된다.The edge bead remover of the present invention may be produced by any method as long as a homogeneous mixture with α-hydroxyisobutyrate, a compound represented by the general formula (I), and an additive acceptable for removing a resist used arbitrarily is obtained.

예를들면, 실온 부근의 온도에서 α-히드록시이소부티르산메틸, 일반식(Ⅰ)로 표시되는 화합물 및 임의로 사용되는 첨가물을 균질하게 되기까지 교반하에 기계적으로 혼합하면 된다.For example, the mixture may be mechanically mixed under stirring until the α-hydroxyisobutyrate, the compound represented by the general formula (I) and the optionally used additive are homogeneous at a temperature near room temperature.

α-히드록시이소부티르산메틸과 일반식(Ⅰ)로 표시되는 화합물의 중량혼합비는 9 : 1∼1 : 9, 보다 바람직하게는 7 : 3∼5 : 5이다.The weight mixing ratio of the alpha -hydroxyisobutyrate and the compound represented by the general formula (I) is 9: 1 to 1: 9, more preferably 7: 3 to 5: 5.

본발명의 엣지비드 리무버는 필요에 따라 다른 용제를 혼합할 수가 있다.The edge bead remover of the present invention can be mixed with other solvents as necessary.

그 용제로서는 에테르류, 에스테르류, 케톤류, 케토에테르류, 케톨류, 알코올류, 알콕시카르복실산류, 디케톤류, 아미드류, 방향족탄화수소 등을 들수가 있다. 이들 용제는 단독으로 또는 2종이상을 조합해서 사용해도 된다.Examples of the solvent include ethers, esters, ketones, ketoethers, ketols, alcohols, alkoxycarboxylic acids, diketones, amides and aromatic hydrocarbons. You may use these solvents individually or in combination of 2 or more types.

본 발명의 엣지비드 리무버는 공지의 포지티브형 레지스트, 네가티브형 레지스트의 어느 것에도 적용할수가 있다.The edge bead remover of the present invention can be applied to any of a known positive resist and a negative resist.

본발명의 엣지비드 리무버가 적용될 수 있는 레지스트의 대표적인 것을 예시하면, 포지티브형에서는 예를들면, 퀴논디아지드계 감광제와 알칼리 가용성수지로된 것, 화학증폭형 레지스트 등이 네가티브형에서는 예를들면, 폴리게피산비닐 등의 감광성기를 갖는 고분자화합물을 함유하는것, 방향족 아지드화합물을 함유하는 것, 혹은 고리화고무와 비스디아지드 화합물로 된 것 등 아지드화합물을 함유하는 것, 디아지드수지를 함유하는 것, 부가중합성 불포화화합물을 함유하는 광중합성조성물, 화학증폭형 네가티브 레지스트 등을 들수가 있다.Illustrative examples of the resist to which the edge bead remover of the present invention can be applied include, for example, the positive type, the quinonediazide-based photosensitive agent and the alkali soluble resin, and the chemically amplified resist, for example, the negative type. Containing azide compounds, such as those containing polymer compounds having photosensitive groups, such as polygepicate, containing aromatic azide compounds, or those consisting of cyclized rubbers and bisdiazide compounds, containing diazide resins And a photopolymerizable composition containing an addition polymerizable unsaturated compound, a chemically amplified negative resist, and the like.

화학증폭형 네가티브 레지스트 등에는 필요에 따라 반사방지막을 형성하는일이 있으나 반사방지막이 유기용제에 가용성인 것이면 불요 반사방지막도 불요 레지스트와 동시에 제거할 수가 있다.The chemically amplified negative resist or the like may be formed with an antireflection film as necessary. However, if the antireflection film is soluble in an organic solvent, the unnecessary antireflection film can be removed simultaneously with the unnecessary resist.

또 피막형성 물질로서는 예를들면, 페놀, 크레솔, 크시레놀등과 알데히드류로부터 얻어지는 노보락수지, 아크릴수지, 스티렌과 아크릴산등과의 혼성중합체, 히드록시스티렌의 중합체, 폴리비닐히드록시벤조에이트, 폴리비닐히드록시벤잘 등의 알칼리 가용성수지가 유효하다.As the film-forming substance, for example, a phenol, cresol, xylenol and the like, a novolak resin obtained from aldehydes, an acrylic resin, a copolymer of styrene and acrylic acid, a polymer of hydroxy styrene, polyvinyl hydroxybenzoate, Alkali-soluble resins, such as polyvinyl hydroxybenzal, are effective.

또 레지스트에는 필요에 따라 상용성 있는 다른 염료, 예를들면, 쿠마린계염료, 아조염료 등을 첨가해도 되고, 다시또 다른 첨가물 예를들면, 용해억제제 등과같이 수지를 개질시키는 부가적수지, 가소제, 안정제, 혹은 현상해서 얻어지는 패턴을 보다 더욱 가시화 하기위한 착색제, 콘트라스트 향상제 등의 관용되는 것을 첨가할수도 있다.In addition, other dyes, for example, coumarin-based dyes and azo dyes, may be added to the resist, if necessary, and further additives such as dissolution inhibitors, additive resins, plasticizers, Commonly used additives such as stabilizers or coloring agents for further visualizing the pattern obtained by developing may be added.

본 발명의 엣지비드 리무버의 적용을 구체적으로 설명하면, 우선 레지스트와 용액은 스핀도포법등 종래로부터 공지의 도포법에의해 필요에따라 전처리된 실리콘기판, 유리기판등에 도포된다.Specifically describing the application of the edge bead remover of the present invention, a resist and a solution are first applied to a silicon substrate, a glass substrate, and the like which have been pretreated as necessary by a conventionally known coating method such as a spin coating method.

도포가 스핀도포법에 의해 행해지는 경우에는 주변부 막의 두께가 중앙부 막의 두께보다도 큰 비드가 형성되고, 또 기판의 둘레변이나 이면부에도 도포물이 퍼지는 것이 보통이다.In the case where the coating is performed by the spin coating method, beads having a larger thickness of the peripheral film than the thickness of the central film are formed, and the coating is usually spread on the circumferential edge or the back surface of the substrate.

본발명의 엣지비드 리무버를 회전하는 주변비드상에 스프레이나 백린스 등의 방법에 의해 도포하므로서 비드의 유동을 촉진시켜 기판상에 실질적으로 균일한 두께를 갖는 레지스트막의 형성을 이룰수가 있다.The edge bead remover of the present invention is applied onto a rotating bead by a method such as spraying or rinsing, thereby facilitating the flow of beads to form a resist film having a substantially uniform thickness on the substrate.

또 기판측면 주변 혹은 배면에 퍼진 레지스트는 엣지비드 리무버의 스프레이에 의해 제거할수가 있다.The resist spread around or on the back side of the substrate can be removed by spraying the edge bead remover.

엣지비드 리무버는 통상 실온부근의 온도에서 엣지비드 및/또는 다른 불요 레지스트 제거에 유효한 양으로 도포된다.Edge bead removers are typically applied in an amount effective to remove edge beads and / or other unnecessary resist at temperatures near room temperature.

제거에 유효한 양은 엣지비드 리무버 및 레지스트의 화학조성, 레지스트 필름의 두께 등 많은 인자에 의존하지만 최적의 양을 결정하는 것은 당업자의 기량의 범위내이다.The effective amount for removal depends on many factors such as edge bead remover and resist chemistry, resist film thickness, etc., but it is within the skill of one in the art to determine the optimum amount.

본발명의 엣지비드 리무버에 의한 레지스트제거는 기판상에 도포된 레지스트필름을 20∼200℃에서 0.1∼120분간 예열한 후에 행해도 된다.The resist removal by the edge bead remover of this invention may be performed after preheating the resist film apply | coated on the board | substrate at 20-200 degreeC for 0.1 to 120 minutes.

본발명의 엣지비드 리무버는 극히 용해성이 우수하기 때문에 상기와 같은 이용형태 외에 예를들면 스핀너컵등에 부착해서 고착된 레지스트의 세정제거에도 유효하게 이용된다.Since the edge bead remover of the present invention is extremely excellent in solubility, it can be effectively used for cleaning and removing resists attached to, for example, spinner cups and the like, in addition to the above-described application forms.

다음에 본 발명을 실시예 및 비교예에 의해 다시또 상세히 설명하지만 본 발명은 이들 실시예에 의해 한정되는 것은 아니다.Next, the present invention will be described in detail again with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

실시예 1∼9 및 비교예 1∼5Examples 1-9 and Comparative Examples 1-5

실리콘 웨이퍼 상에 시판의 포토레지스트(도쿄오카제, TFR-790)를 스핀너에의해 건조막두께가 16000Å이 되도록 도포한 후 건조오븐으로 120℃로 30분간 예열하여 레지스트막을 형성했다.A commercially available photoresist (TFR-790, manufactured by Tokyo Okuka) was applied onto a silicon wafer so as to have a dry film thickness of 16000 Pa by a spinner, and then preheated at 120 ° C. for 30 minutes with a dry oven to form a resist film.

이어서 표에 나타내는 조성의 각 용제 100ml를 비커에 넣고, 상기에서 작성한 웨이퍼를 10초간 용제에 침지시킴 후 건져 올리고나서 바로 송풍기로 건조를 행하여, 각 웨이퍼의 막두께(Å)를 막두께 측정계(나노메트릭·재팬사제, 나노스펙M 5000)로 측정하므로서 용해속도(Å/sec)를 구했다.Subsequently, 100 ml of each solvent having the composition shown in the table was placed in a beaker, the wafer prepared above was immersed in the solvent for 10 seconds, then pulled up, dried immediately by a blower, and the film thickness of each wafer was measured by a film thickness gauge (nano Dissolution rate (Å / sec) was calculated | required by measuring with the metric Japan company make, Nanospec M 5000.

실시예 및 비교예의 결과를 표 1에 나타낸다.Table 1 shows the results of Examples and Comparative Examples.

또한 비교예 1∼3 및 5는 실제로 엣지비드 리무버로서 사용되고 있는 용제이다.In addition, Comparative Examples 1-3 and 5 are the solvents actually used as an edge bead remover.

표 1Table 1

엣지비드 리무버의화학적조성(중량비)Chemical Composition of Edge Bead Remover (Weight Ratio) 용해속도(Å/sec)Dissolution rate (Å / sec) 냄새smell 실시예 1Example 1 HBM:PGME=5:5HBM: PGME = 5: 5 14821482 불쾌한냄새 없음No unpleasant smell 실시예 2Example 2 HBM:PGME=6:4HBM: PGME = 6: 4 13901390 불쾌한냄새 없음No unpleasant smell 실시예 3Example 3 HBM:PGME=7:3HBM: PGME = 7: 3 867867 불쾌한냄새 없음No unpleasant smell 실시예 4Example 4 HBM:PGMEA=5:5HBM: PGMEA = 5: 5 11521152 불쾌한냄새 없음No unpleasant smell 실시예 5Example 5 HBM:PGMEA=6:4HBM: PGMEA = 6: 4 10861086 불쾌한냄새 없음No unpleasant smell 실시예 6Example 6 HBM:PGMEA=7:3HBM: PGMEA = 7: 3 673673 불쾌한냄새 없음No unpleasant smell 실시예 7Example 7 HBM:PGME=5:5HBM: PGME = 5: 5 776776 불쾌한냄새 없음No unpleasant smell 실시예 8Example 8 HBM:PGME=6:4HBM: PGME = 6: 4 758758 불쾌한냄새 없음No unpleasant smell 실시예 9Example 9 HBM:PGME=7:3HBM: PGME = 7: 3 498498 불쾌한냄새 없음No unpleasant smell 비교예 1Comparative Example 1 PGMEPGME 15171517 불쾌한냄새 있음Unpleasant smell 비교예 2Comparative Example 2 PGMEAPGMEA 669669 불쾌한냄새 있음Unpleasant smell 비교예 3Comparative Example 3 락트산에틸Ethyl lactate 701701 독특한냄새Peculiar smell 비교예 4Comparative Example 4 HBMHBM 247247 불쾌한냄새 있음Unpleasant smell 비교예 5Comparative Example 5 AcOBuAcOBu 14811481 독특한냄새Peculiar smell

HBM: α-히드록시이소부티르산메틸HBM: α-hydroxyisobutyrate methyl

PGME: 프로필렌글리콜 모노메틸에테르PGME: propylene glycol monomethyl ether

PGMEA: 프로필렌글리콜 모노메틸에테르아세테이트PGMEA: propylene glycol monomethyl ether acetate

AcOBu: 아세트산부틸AcOBu: Butyl acetate

본 발명의 엣지비드 리무버는 우수한 용해속도를 갖고 독성이 극히 낮고, 생분해성이 있기 때문에 자연계에 대한 축적이 없고 환경보전에 바람직하다.Since the edge bead remover of the present invention has excellent dissolution rate, extremely low toxicity, and biodegradability, there is no accumulation in nature and is preferable for environmental conservation.

또 증발속도가 적당한 값이며, 양호한 건조성을 가지면서 인화점이 비교적 높고, 불쾌한 냄새도 극히 적기 때문에 작업성이나 안전성이 높은 이점이 있다.In addition, the evaporation rate is an appropriate value, has a good drying property, a relatively high flash point, and extremely low unpleasant odors, and thus has the advantage of high workability and safety.

Claims (10)

α-히드록시이소부티르산메틸 및 하기 일반식 (Ⅰ) :methyl α-hydroxyisobutyrate and the following general formula (I): R1 R 1 ｜｜ RO-(CHCH2O)n-R2(Ⅰ)RO- (CHCH 2 O) n -R 2 (I) (R는 수소 또는 아세틸기, R1은 수소 또는 메틸기, R2는 탄소수 1∼4의 알킬기, n은 0∼3의 정수를 나타낸다. 단 R이 수소를 나타낼 때 n은 1∼3의 정수를 나타낸다) 로 표시되는 화합물로 된 혼합물인 것을 특징으로 하는 엣지비드 리무버(R is hydrogen or an acetyl group, R 1 is hydrogen or methyl group, R 2 is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 3. However, when R represents hydrogen, n is an integer of 1 to 3 Edge bead remover, characterized in that the mixture of the compound represented by 제1항에 있어서,The method of claim 1, α-히드록시이소부티르산메틸 및 상기 일반식 (Ⅰ)로 표시되는 화합물과의 중량혼합비가 9 : 1∼1 : 9인 것을 특징으로하는 엣지비드 리무버.An edge bead remover, wherein the weight mixing ratio of the α-hydroxyisobutyrate methyl and the compound represented by the general formula (I) is from 9: 1 to 1: 9. 제1항 또는 제2항에 있어서,The method according to claim 1 or 2, 상기한 일반식(Ⅰ)로 표시되는 화합물이 글리콜모노알킬에테르, 글리콜모노알킬에테르아세테이트 및 아세트산에스테르로된 군으로부터 선택되는 적어도 하나의 화합물인 것을 특징으로 하는 엣지비드 리무버.An edge bead remover, wherein the compound represented by the general formula (I) is at least one compound selected from the group consisting of glycol monoalkyl ether, glycol monoalkyl ether acetate, and acetate ester. 제3항에 있어서,The method of claim 3, 상기한 글리콜모노알킬에테르가 디에틸렌글리콜 모노메틸에테르, 디에틸렌글리콜 모노에틸에테르, 디에틸렌글리콜 모노부틸에테르, 트리에틸렌글리콜 모노메틸에테르, 트리에틸렌글리콜 모노에틸에테르, 트리에틸렌글리콜 모노부틸에테르, 프로필렌글리콜 모노메틸에테르, 프로필렌글리콜 모노에틸에테르, 프로필렌글리콜 모노부틸에테르, 디프로필렌글리콜 모노메틸에테르, 디프로필렌글리콜 모노에틸에테르 및 디프로필렌글리콜 모노부틸에테르로된 군으로부터 선택된 적어도 하나의 화합물인 것을 특징으로 하는 엣지비드 리무버.The above-mentioned glycol monoalkyl ether is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene At least one compound selected from the group consisting of glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Edge bead remover. 제3항 또는 제4항에 있어서,The method according to claim 3 or 4, 상기한 글리콜모노알킬에테르가 프로필렌글리콜 모노메틸에테르인 것을 특징으로 하는 엣지비드 리무버.An edge bead remover, wherein the glycol monoalkyl ether is propylene glycol monomethyl ether. 제3항에 있어서,The method of claim 3, 글리콜모노알킬에테르아세테이트가 디에틸렌글리콜 모노메틸에테르아세테이트, 디에틸렌글리콜 모노에틸에테르아세테이트, 디에틸렌글리콜 모노부틸에테르아세테이트, 프로필렌글리콜 모노메틸에테르아세테이트, 프로필렌글리콜 모노에틸에테르아세테이트 및 프로필렌글리콜 모노부틸에테르아세테이트로된 군으로부터 선택된 적어도 하나의 화합물인 것을 특징으로 하는 엣지비드 리무버.Glycol monoalkyl ether acetate is diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate Edge bead remover, characterized in that at least one compound selected from the group consisting of. 제3항 또는 제6항에 있어서,The method according to claim 3 or 6, wherein 상기한 글리콜모노알킬에테르아세테이트가 프로필렌글리콜 모노메틸에테르아세테이트인 것을 특징으로 하는 엣지비드 리무버.An edge bead remover, wherein said glycol monoalkyl ether acetate is propylene glycol monomethyl ether acetate. 제3항에 있어서,The method of claim 3, 상기한 아세트산에스테르가, 아세트산메틸, 아세트산에틸 및 아세트산부틸로된 군으로부터 선택된 적어도 하나의 화합물인 것을 특징으로 하는 엣지비드 리무버.The above-mentioned acetate ester is at least one compound chosen from the group which consists of methyl acetate, ethyl acetate, and butyl acetate, The edge bead remover characterized by the above-mentioned. 제3항 또는 제8항에 있어서,The method according to claim 3 or 8, 아세트산에스테르가 아세트산부틸인 것을 특징으로 하는 엣지비드 리무버.An edge bead remover, wherein the acetate ester is butyl acetate. 레지스트형성용 도포물을 기판에 도포하고 및 기판의 주변부, 주변부 및/또는 이면부에 부착한 불필요한 레지스트 형성 조성물을 청구항 1에 기재된 엣지비드 리무버를 사용해서 제거하는 단계로 된 것을 특징으로 하는 불필요한 레지스트 형성 조성물의 제거방법.Applying a resist-forming coating to the substrate and removing unnecessary resist-forming compositions attached to the periphery, the periphery and / or the back of the substrate using the edge bead remover according to claim 1; Method of removing the forming composition.
KR1020000082464A 1999-12-28 2000-12-27 Edge bead remover KR100733650B1 (en)

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