JP2008058623A - Photoresist stripping liquid, and substrate tratment method using the same - Google Patents
Photoresist stripping liquid, and substrate tratment method using the same Download PDFInfo
- Publication number
- JP2008058623A JP2008058623A JP2006235654A JP2006235654A JP2008058623A JP 2008058623 A JP2008058623 A JP 2008058623A JP 2006235654 A JP2006235654 A JP 2006235654A JP 2006235654 A JP2006235654 A JP 2006235654A JP 2008058623 A JP2008058623 A JP 2008058623A
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- Prior art keywords
- photoresist
- mass
- stripping solution
- substrate
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000758 substrate Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 8
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
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- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229960001855 mannitol Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DLEZVOPJBSAAGW-UHFFFAOYSA-N methyl benzotriazole-1-carboxylate Chemical compound C1=CC=C2N(C(=O)OC)N=NC2=C1 DLEZVOPJBSAAGW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- XVHLHUNZWRKZPF-UHFFFAOYSA-N n-[(4-methylbenzotriazol-1-yl)methyl]-n-propan-2-ylpropan-2-amine Chemical compound C1=CC=C2N(CN(C(C)C)C(C)C)N=NC2=C1C XVHLHUNZWRKZPF-UHFFFAOYSA-N 0.000 description 1
- RUFMRRIYNIOMBR-UHFFFAOYSA-N n-ethyl-n-[(4-methylbenzotriazol-1-yl)methyl]ethanamine Chemical compound C1=CC=C2N(CN(CC)CC)N=NC2=C1C RUFMRRIYNIOMBR-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
本発明は、フォトレジスト用剥離液に関する。特に、ICやLSIなどの半導体素子あるいは液晶パネル素子の製造に好適に使用される、剥離性に優れるフォトレジスト用剥離液、さらにはこれを用いた基板の処理方法に関する。 The present invention relates to a photoresist stripping solution. In particular, the present invention relates to a photoresist stripping solution excellent in peelability, which is preferably used in the manufacture of semiconductor elements such as IC and LSI, or liquid crystal panel elements, and a substrate processing method using the same.
ICやLSIなどの半導体素子や液晶パネル素子の製造は、まず、シリコンウェハ、ガラスなどの基板上にCVD蒸着された導電性金属膜やSiO2膜などの絶縁膜を形成する。次に、上記導電性金属膜や絶縁膜上に、フォトレジストを均一に塗布し、これを選択的に露光、現像処理してフォトレジストパターンを形成する。そして、このパターンをマスクとして上記導電性金属膜や絶縁膜を選択的にエッチングし、微細回路を形成した後、不要のフォトレジスト層を剥離液で除去して製造される。かかる不要のフォトレジスト層除去には、従来、安全性、剥離性の点から種々の有機系剥離液が用いられてきた(特許文献1参照)。 In the manufacture of semiconductor elements such as IC and LSI and liquid crystal panel elements, first, an insulating film such as a conductive metal film or a SiO 2 film formed by CVD deposition is formed on a substrate such as a silicon wafer or glass. Next, a photoresist is uniformly applied on the conductive metal film or the insulating film, and this is selectively exposed and developed to form a photoresist pattern. Then, the conductive metal film and the insulating film are selectively etched using this pattern as a mask to form a fine circuit, and then an unnecessary photoresist layer is removed with a stripping solution. Conventionally, various organic stripping solutions have been used for removing the unnecessary photoresist layer from the viewpoints of safety and stripping (see Patent Document 1).
他方、上記CVD蒸着された導電性金属膜の材料として、アルミニウム(Al);アルミニウム−ケイ素(Al−Si)、アルミニウム(Al−Cu)、アルミニウム−ケイ素−銅(Al−Si−Cu)などのアルミニウム合金(Al);チタン(Ti);チタンナイトライド(TiN)、チタンタングステン(TiW)などのチタン合金(Ti合金);タンタル(Ta)、窒化タンタル(TaN)、タングステン(W)、窒化タングステン(WN)、銅(Cu)などが用いられ、これらは単層〜複数層にて基板上に形成される。
しかしながら、特許文献1に記載されているフォトレジスト用剥離液は、水溶性有機溶媒であるグリコールモノアルキルエーテルの含有量が1〜30質量%と少ないため、レジストの溶解性が低いという問題があった。 However, the photoresist stripping solution described in Patent Document 1 has a problem that resist solubility is low because the content of glycol monoalkyl ether, which is a water-soluble organic solvent, is as low as 1 to 30% by mass. It was.
さらに、フォトレジスト用剥離液の特性として、導電性金属膜の腐食を防止する一方で、エッチングにより形成された金属残渣は除去する必要がある、という同種類の金属に対して相反する特性が求められていた。 Furthermore, as a property of the stripping solution for photoresist, there is a demand for a conflicting property with respect to the same type of metal that it is necessary to remove the metal residue formed by etching while preventing the corrosion of the conductive metal film. It was done.
本発明は以上のような課題に鑑みてなされたものであり、少なくとも導電性金属膜としてアルミニウムを含む金属層が形成された基板に対して腐食を発生せず、かつ効果的にフォトレジスト膜を除去することが可能なフォトレジスト用剥離液を提供することを目的とする。 The present invention has been made in view of the above problems, and at least does not cause corrosion on a substrate on which a metal layer containing aluminum is formed as a conductive metal film, and effectively forms a photoresist film. It is an object of the present invention to provide a photoresist stripping solution that can be removed.
本発明者らは上記課題を解決するために、フォトレジスト用剥離液に含有される成分の配合量に着目して鋭意研究を重ねた。その結果、各成分を所定の配合量で含有させることで、上記課題を解決できることを見出し、本発明を完成するに至った。より具体的には、本発明は、以下のようなものを提供する。 In order to solve the above-mentioned problems, the inventors of the present invention have made extensive studies focusing on the amount of components contained in the photoresist stripping solution. As a result, it has been found that the above problems can be solved by containing each component in a predetermined blending amount, and the present invention has been completed. More specifically, the present invention provides the following.
(A)糖アルコールを0.1質量%以上10質量%以下、(B)アルカノールアミンを3質量%以上20質量%以下、(C)水を5質量%以上40質量%以下、および(D)水溶性有機溶剤を60質量%以上95質量%以下含有するフォトレジスト用剥離液を提供する。 (A) 0.1% to 10% by weight of sugar alcohol, (B) 3% to 20% by weight of alkanolamine, (C) 5% to 40% by weight of water, and (D) A photoresist stripping solution containing 60% by mass or more and 95% by mass or less of a water-soluble organic solvent is provided.
また、アルミニウムを含む金属層が形成された基板上のフォトレジストの剥離に用いる上記フォトレジスト用剥離液を提供する。 The present invention also provides the photoresist stripping solution used for stripping a photoresist on a substrate on which a metal layer containing aluminum is formed.
また、アルミニウムを含む金属層が形成された基板上にフォトレジスト膜を形成し、該フォトレジスト膜を露光、現像処理し、続いて該基板をドライエッチング加工し、さらに前記フォトレジスト膜の残留物およびエッチング残渣物を上記フォトレジスト用剥離液により洗浄除去する工程を含む基板の処理方法を提供する。 Further, a photoresist film is formed on the substrate on which the metal layer containing aluminum is formed, the photoresist film is exposed and developed, and then the substrate is dry-etched, and the photoresist film residue is further formed. And a substrate processing method including a step of cleaning and removing the etching residue by the photoresist stripping solution.
本発明のフォトレジスト用剥離液は、特に、少なくとも導電性金属膜としてアルミニウムを含む金属層が形成された基板に対して、さらにはその他の金属を含む金属層が形成された基板に対しても腐食を発生せず、かつ効果的にフォトレジスト膜を除去することが可能である。 The photoresist stripping solution of the present invention is particularly suitable for a substrate on which a metal layer containing aluminum is formed as at least a conductive metal film, and also on a substrate on which a metal layer containing other metals is formed. It is possible to remove the photoresist film effectively without causing corrosion.
本発明のフォトレジスト用剥離液(以下、「剥離液」ともいう。)は、(A)糖アルコールを0.1質量%以上10質量%以下、(B)アルカノールアミンを3質量%以上20質量%以下、(C)水を5質量%以上40質量%以下、および(D)水溶性有機溶剤を60質量%以上95質量%以下含有するフォトレジスト用剥離液である。以下、各成分について説明する。 The stripping solution for photoresist of the present invention (hereinafter also referred to as “stripping solution”) is (A) 0.1% by mass to 10% by mass of sugar alcohol, and (B) 3% by mass to 20% by mass of alkanolamine. % Or less, (C) 5% by mass to 40% by mass of water, and (D) 60% by mass to 95% by mass of a water-soluble organic solvent. Hereinafter, each component will be described.
<(A)糖アルコール>
本発明の剥離液は、糖アルコール(以下、「(A)成分」ともいう。)を含有する。糖アルコールを配合することにより、基板上に形成されたアルミニウムを含む金属層の腐食を防止することができる。糖アルコールは、一般にCn(H2O)m(nおよびmは、0以上の整数)で表されるいわゆる糖のカルボニル基を還元して得られる。具体的には、D−ソルビトール、アラビトール、マンニトール、キシリトール、エリトリトール、D−トレイトール、L−アラビニトール、リビトール、D−グルシトール、ガラクチトール、L−ラムニトール、ショ糖、でんぷんなどが挙げられる。中でも、キシリトール、D−ソルビトールが好ましく用いられる。また、糖アルコールは、1種または2種以上を組み合わせて用いることができる。
<(A) Sugar alcohol>
The stripping solution of the present invention contains a sugar alcohol (hereinafter also referred to as “component (A)”). By blending the sugar alcohol, corrosion of the metal layer containing aluminum formed on the substrate can be prevented. The sugar alcohol is generally obtained by reducing a so-called sugar carbonyl group represented by C n (H 2 O) m (n and m are integers of 0 or more). Specific examples include D-sorbitol, arabitol, mannitol, xylitol, erythritol, D-threitol, L-arabinitol, ribitol, D-glucitol, galactitol, L-rhamnitol, sucrose, starch, and the like. Of these, xylitol and D-sorbitol are preferably used. Moreover, sugar alcohol can be used 1 type or in combination of 2 or more types.
(A)成分の配合量は剥離溶液中0.1質量%以上10質量%以下である。より好ましくは0.5質量%以上5質量%以下である。(A)成分の配合量を上記範囲とすることにより、金属層、特にアルミニウム層に対して優れた防食性能を得ることができる。 (A) The compounding quantity of a component is 0.1 to 10 mass% in stripping solution. More preferably, it is 0.5 mass% or more and 5 mass% or less. By making the compounding quantity of (A) component into the said range, the anticorrosion performance excellent with respect to the metal layer, especially the aluminum layer can be obtained.
<(B)アルカノールアミン>
アルカノールアミン(以下、「(B)成分」ともいう。)としては、例えばモノエタノールアミン、N−メチルエタノールアミン、N−エチルエタノールアミン、N−プロピルエタノールアミン、N−ブチエタノールアミン、ジエタノールアミン、モノイソプロパノールアミン、N−メチルイソプロパノールアミン、N−エチルイソプロパノールアミン、N−プロピルイソプロパノールアミン、2−アミノプロパン−1−オール、N−メチル−2−アミノ−プロパン−1−オール、N−エチル−2−アミノ−プロパン−1−オール、1−アミノプロパン−3−オール、N−メチル−1−アミノプロパン−3−オール、N−エチル−1−アミノプロパン−3−オール、1−アミノブタン−2−オール、N−メチル−1−アミノブタン−2−オール、N−エチル−1−アミノブタン−2オール、2−アミノブタン−1−オール、N−メチル−2−アミノブタン−1−オール、N−エチル−2−アミノブタン−1−オール、3−アミノブタン−1−オール、N−メチル−3−アミノブタン−1−オール、N−エチル−3−アミノブタン−1−オール、1−アミノブタン−4−オール、N−メチル1−アミノブタン−4−オール、N−エチル−1−アミノブタン−4−オール、1−アミノ−2−メチルプロパン−2−オール、2−アミノ−2−メチルプロパン−1−オール、1−アミノペンタン−4−オール、2−アミノ−4−メチルペンタン−1−オール、2−アミノヘキサン−1−オール、3−アミノヘプタン−4−オール、1−アミノオクタン−2−オール、5−アミノオクタン−4−オール、1−アミノプパン−2,3−ジオール、2−アミノプロパン−1,3−ジオール、トリス(オキシメチル)アミノメタン、1,2−ジアミノプロパン−3−オール、1,3−ジアミノプロパン−2−オール、2−(2−アミノエトキシ)エタノールなどが挙げられる。中でもモノイソプロパノールアミン、ジグリコールアミン、N−メチルエタノールアミン、の中から選ばれる少なくとも1種が好ましく、特にモノエタノールアミンは、他のアルカノールアミンと比較し、アルミニウムに対する腐食が少ないため、最も好ましく用いられる。(B)成分は1種または2種以上を組み合わせて用いることができる。
<(B) Alkanolamine>
Examples of the alkanolamine (hereinafter also referred to as “component (B)”) include monoethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butyethanolamine, diethanolamine, and monoethanolamine. Isopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-ol, N-ethyl-2- Amino-propan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol N-methyl-1-aminobutane-2-o N-ethyl-1-aminobutane-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutane-1- All, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutane-4-ol, N-methyl 1-aminobutane-4-ol, N-ethyl-1 -Aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentane -1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctane-2-ol, 5-aminooctane-4 Ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris (oxymethyl) aminomethane, 1,2-diaminopropane-3-ol, 1,3-diaminopropane-2 -Ol, 2- (2-aminoethoxy) ethanol and the like. Among these, at least one selected from monoisopropanolamine, diglycolamine, and N-methylethanolamine is preferable. Monoethanolamine is most preferably used because it has less corrosion to aluminum than other alkanolamines. It is done. (B) A component can be used 1 type or in combination of 2 or more types.
(B)成分の配合量は、剥離液中1質量%以上20質量%以下である。より好ましくは3質量%以上10質量%以下である。(B)成分の配合量を上記範囲とすることにより、優れたフォトレジスト層の剥離性能を得ることができる。 (B) The compounding quantity of a component is 1 to 20 mass% in stripping solution. More preferably, it is 3 mass% or more and 10 mass% or less. By setting the blending amount of the component (B) within the above range, excellent peeling performance of the photoresist layer can be obtained.
<(C)水>
水(以下、「(C)成分」ともいう。)は、本発明のフォトレジスト剥離液中の他成分中に必然的に含まれているものであるが、さらに加えてその量を調整する。(C)成分の配合量は、剥離液中5質量%以上40質量%以下である。より好ましくは10質量%以上30質量%以下である。(C)成分の配合量を上記範囲とすることにより、フォトレジスト層、残渣物に対する優れた剥離性能、および、アルミニウムなどの金属層に対する防食性能を得ることができる。また、上記範囲内とすることにより、糖アルコールを剥離液中に溶解させることができる。
<(C) Water>
Water (hereinafter also referred to as “component (C)”) is inevitably contained in the other components in the photoresist stripping solution of the present invention, but the amount thereof is further adjusted. (C) The compounding quantity of a component is 5 to 40 mass% in stripping solution. More preferably, it is 10 mass% or more and 30 mass% or less. By setting the blending amount of the component (C) within the above range, excellent peeling performance for the photoresist layer and residue, and anticorrosion performance for a metal layer such as aluminum can be obtained. Moreover, sugar alcohol can be dissolved in peeling liquid by setting it as the said range.
<(D)水溶性有機溶剤>
水溶性有機溶剤(以下、「(D)成分」ともいう。)としては、水と混和性のある有機溶剤であればよく、他の配合成分を溶解させるものであれば特に限定されず、任意に使用することができる。このような水溶性有機溶剤としては、ジメチルスルホキシドなどのスルホキシド類;ジメチルスルホン、ジエチルスルホン、ビス(2−ヒドロキシエチル)スルホン、テトラメチレンスルホンなどのスルホン類;N,N−ジメチルホルムアミド、N−メチルホルムアミド、N,N−ジメチルアセトアミド、N−メチルアセトアミド、N,N−ジエチルアセトアミドなどのアミド類;N−メチル−2−ピロリドン、N−エチル−2−ピロリドン、N−プロピル−2−ピロリドン、N−ヒドロキシメチル−2−ピロリドン、N−ヒドロキシエチル−2−ピロリドンなどのラクタム類;1,3−ジメチル−2−イミダゾリジノン、1,3−ジエチル−2−イミダゾリジノン、1,3−ジイソプロピル−2−イミダゾリジノンなどのイミダゾリジノン類;エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテルなどのジエチレングリコールモノアルキルエーテル(アルキルは炭素原子数1〜6の低級アルキル)、およびその誘導体が挙げられる。中でも、ジエチレングリコールモノブチルエーテル、N−メチル−2−ピロリドン、ジメチルスルホキシドの中から選ばれる少なくとも1種が、フォトレジスト剥離性向上の点から好ましい。(C)成分は1種または2種以上を組み合わせて用いることができる。
<(D) Water-soluble organic solvent>
The water-soluble organic solvent (hereinafter also referred to as “component (D)”) is not particularly limited as long as it is an organic solvent miscible with water and can dissolve other compounding components. Can be used for Examples of such water-soluble organic solvents include sulfoxides such as dimethyl sulfoxide; sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, and tetramethylene sulfone; N, N-dimethylformamide, N-methyl Amides such as formamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N -Lactams such as hydroxymethyl-2-pyrrolidone and N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl 2-Imidazolidinones such as imidazolidinone Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol Examples include diethylene glycol monoalkyl ethers such as monobutyl ether (alkyl is a lower alkyl having 1 to 6 carbon atoms), and derivatives thereof. Among these, at least one selected from diethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, and dimethyl sulfoxide is preferable from the viewpoint of improving the photoresist peelability. (C) A component can be used 1 type or in combination of 2 or more types.
(D)成分の配合量は、剥離液中60質量%以上95質量%以下である。より好ましくは65質量%以上80質量%以下である。(D)成分の配合量を上記範囲とすることにより、高いレジスト溶解性を有することができるため、優れたフォトレジスト層の剥離性能を得ることができる。また、(D)成分の配合量を多くすることにより、溶剤の蒸留精製が行いやすくなるため、溶剤の再生回収が容易になり、剥離液のコストを低減することができる。 (D) The compounding quantity of a component is 60 to 95 mass% in stripping solution. More preferably, it is 65 mass% or more and 80 mass% or less. By setting the blending amount of the component (D) within the above range, high resist solubility can be obtained, and thus excellent photoresist layer peeling performance can be obtained. Moreover, since the solvent is easily purified by distillation by increasing the amount of component (D), the solvent can be easily recovered and recovered, and the cost of the stripping solution can be reduced.
また、本発明の剥離液では、上記(A)〜(D)成分を上記配合量で含有することにより、所望の効果を奏することができるが、所望によりさらに防食剤を配合してもよい。このような防食剤としては還元性を有する防食剤、吸着性を有する防食剤、還元性および吸着性を併せ持つ防食剤の3種に分類することができる。 Moreover, in the peeling liquid of this invention, although a desired effect can be show | played by containing the said (A)-(D) component with the said compounding quantity, you may mix | blend an anticorrosive agent as needed. Such an anticorrosive agent can be classified into three types: an anticorrosive agent having a reducing property, an anticorrosive agent having an adsorbing property, and an anticorrosive agent having both reducing and adsorbing properties.
前記還元性を有する防食剤としては、ピロカテコール、tert−ブチルカテコール、ピロガロール、没食子酸などの芳香族ヒドロキシ化合物を挙げることができる。 Examples of the anticorrosive having reducibility include aromatic hydroxy compounds such as pyrocatechol, tert-butylcatechol, pyrogallol, and gallic acid.
さらに、前記吸着性を有する防食剤としては、ベンゾトリアゾール、5,6−ジメチルベンゾトリアゾール、1−ヒドロキシベンゾトリアゾール、1−メチルベンゾトリアゾール、1−アミノベンゾトリアゾール、1−フェニルベンゾトリアゾール、1−ヒドロキシメチルベンゾトリアゾール、1−ベンゾトリアゾールカルボン酸メチル、5−ベンゾトリアゾールカルボン酸、1−メトキシ−ベンゾトリアゾール、1−(2,2−ジヒドロキシエチル)−ベンゾトリアゾール、1−(2,3−ジヒドロキシプロピル)ベンゾトリアゾール、あるいは「イルガメット」シリーズとしてチバ・スペシャリティー・ケミカルズ社より市販されている、2,2'−{[(4−メチル−1H−ベンゾトリアゾール−1−イル)メチル]イミノ}ビスエタノール、2,2'−{[(5−メチル−1H−ベンゾトリアゾール−1−イル)メチル]イミノ}ビスエタノール、2,2'−{[(4−メチル−1H−ベンゾトリアゾール−1−イル)メチル]イミノ}ビスエタン、または2,2'−{[(4−メチル−1H−ベンゾトリアゾール−1−イル)メチル]イミノ}ビスプロパンなどのトリアゾール系化合物を挙げることができる。 Further, as the anticorrosive having the adsorptivity, benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxy Methylbenzotriazole, methyl 1-benzotriazolecarboxylate, 5-benzotriazolecarboxylic acid, 1-methoxy-benzotriazole, 1- (2,2-dihydroxyethyl) -benzotriazole, 1- (2,3-dihydroxypropyl) 2,2 ′-{[(4-Methyl-1H-benzotriazol-1-yl) methyl] imino} bisethano commercially available from Ciba Specialty Chemicals as benzotriazole or “Irgamet” series 2,2 ′-{[(5-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol, 2,2 ′-{[(4-methyl-1H-benzotriazole-1- Yl) methyl] imino} bisethane or 2,2 ′-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino} bispropane.
還元性と表面吸着性を併せ持つ防食剤としては、1−チオグリセロール、2−メルカプトエタノールなどのメルカプト基含有化合物を挙げることができる。 Examples of the anticorrosive having both reducing property and surface adsorptivity include mercapto group-containing compounds such as 1-thioglycerol and 2-mercaptoethanol.
前記防食剤の中でも、水酸基若しくはメルカプト基含有化合物を含有する防食剤が好ましく、中でも芳香族ヒドロキシ化合物およびメルカプト基含有化合物の中から選ばれる少なくとも1種が、防食性能が高いという観点から好ましい。このような防食性能の高い防食剤を選択することにより、微量の添加で所望の防食性能が得られることから、本発明剥離液を回収し、蒸留再生可能とすることができる。 Among the anticorrosives, an anticorrosive containing a hydroxyl group or a mercapto group-containing compound is preferable, and among them, at least one selected from an aromatic hydroxy compound and a mercapto group-containing compound is preferable from the viewpoint of high anticorrosion performance. By selecting such an anticorrosive having a high anticorrosion performance, the desired anticorrosion performance can be obtained with a small amount of addition. Therefore, the stripping solution of the present invention can be recovered and made recyclable by distillation.
本発明の剥離液は、ネガ型およびポジ型フォトレジストを含めてアルカリ水溶液で現像可能なフォトレジストに有利に使用できる。このようなフォトレジストとしては、(i)ナフトキノンジアジド化合物とノボラック樹脂を含有するポジ型フォトレジスト、(ii)露光により酸を発生する化合物、酸により分解しアルカリ水溶液に対する溶解性が増大する化合物およびアルカリ可溶性樹脂を含有するポジ型フォトレジスト、(iii)露光により酸を発生する化合物、酸により分解しアルカリ水溶液に対する溶解性が増大する基を有するアルカリ可溶性樹脂を含有するポジ型フォトレジスト、および(iv)光により酸を発生する化合物、架橋剤およびアルカリ可溶性樹脂を含有するネガ型フォトレジストなどが挙げられるが、これらに限定されるものではない。 The stripping solution of the present invention can be advantageously used for photoresists that can be developed with an aqueous alkaline solution, including negative and positive photoresists. Examples of such a photoresist include (i) a positive photoresist containing a naphthoquinonediazide compound and a novolac resin, (ii) a compound that generates an acid upon exposure, a compound that is decomposed by an acid and has increased solubility in an alkaline aqueous solution, and A positive photoresist containing an alkali-soluble resin, (iii) a compound that generates an acid upon exposure, a positive photoresist containing an alkali-soluble resin having a group that is decomposed by an acid and increases the solubility in an aqueous alkali solution, and ( iv) Examples include, but are not limited to, compounds that generate an acid by light, a negative photoresist containing a crosslinking agent and an alkali-soluble resin, and the like.
本発明の剥離液の使用態様は、フォトリソグラフィー法により得られたフォトレジストパターンを形成し、これをマスクとして導電性金属膜(特には、アルミニウムを含む金属層)や絶縁膜を選択的にエッチングし、微細回路を形成した後フォトレジストパターンおよびエッチングによる残渣物を剥離する。 The use mode of the stripping solution of the present invention is that a photoresist pattern obtained by a photolithography method is formed, and a conductive metal film (particularly, a metal layer containing aluminum) or an insulating film is selectively etched using the photoresist pattern as a mask. Then, after forming the fine circuit, the photoresist pattern and the residue due to etching are peeled off.
フォトレジスト層の形成、露光、現像、およびエッチング処理は、いずれも慣用的な手段であり、特に限定されない。また、エッチングはウェットエッチング、ドライエッチングのいずれも用いることができる。 The formation, exposure, development, and etching treatment of the photoresist layer are all conventional means and are not particularly limited. As the etching, either wet etching or dry etching can be used.
本発明の剥離液を用いた剥離処理は通常、浸漬法、シャワー法により施される。剥離時間は、剥離される十分な時間であればよく、特に限定されるものではないが、より短時間で剥離処理可能なものが好ましい。 The stripping treatment using the stripping solution of the present invention is usually performed by an immersion method or a shower method. The peeling time is not particularly limited as long as it is a sufficient time for peeling, but is preferably one that can be peeled in a shorter time.
なお剥離処理を行った後、慣用的に施されている純水や低級アルコールなどを用いたリンス処理および乾燥処理を施してもよい。 In addition, after performing a peeling process, you may perform the rinse process and drying process using the pure water, lower alcohol, etc. which are conventionally performed.
以下、本発明の実施例を説明するが、これら実施例は本発明を好適に説明するための例示に過ぎず、なんら本発明を限定するものではない。 Examples of the present invention will be described below. However, these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.
(実施例1〜6、比較例1〜5)
[フォトレジスト膜の剥離性]
TFT用フォトレジストであるTFR−H(東京応化工業(株)製)をウェハ上にパターニングし、150℃にて90秒間ポストベークを施した。このレジストパターンを有するウェハを、50℃に加熱した下記表1に示すフォトレジスト用剥離液に2分間浸漬し、レジストの剥離性をSEM写真により観察し、下記評価基準により評価した。結果を表1に示す。
(Examples 1-6, Comparative Examples 1-5)
[Removability of photoresist film]
A TFT photoresist TFR-H (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was patterned on the wafer and post-baked at 150 ° C. for 90 seconds. The wafer having this resist pattern was immersed in a photoresist stripping solution shown in Table 1 heated to 50 ° C. for 2 minutes, the resist stripping property was observed with an SEM photograph, and evaluated according to the following evaluation criteria. The results are shown in Table 1.
(評価)
○:完全に除去された。
△:一部残存物が認められた。
×:大部分が残存していた。
(Evaluation)
○: Completely removed.
Δ: Some residue was observed.
X: Most remained.
[Al防食性(浸漬法)]
Alを形成したウェハを、下記表1に示すフォトレジスト用剥離液に50℃、30分間浸漬処理し、シート抵抗値を測定した。その結果からAlのエッチング量(腐食量)を求め、Alに対する防食性を下記評価基準により評価した。結果を表1に示す。なお、シート抵抗値の測定は、VR−70(国際電気(株)製)を用いて測定した。
[Al anticorrosion (dipping method)]
The wafer on which Al was formed was immersed in a photoresist stripping solution shown in Table 1 below at 50 ° C. for 30 minutes, and the sheet resistance value was measured. From the results, the etching amount (corrosion amount) of Al was obtained, and the anticorrosion properties against Al were evaluated according to the following evaluation criteria. The results are shown in Table 1. The sheet resistance value was measured using VR-70 (made by Kokusai Electric Co., Ltd.).
(評価)
○:腐食は全くみられなかった。
△:腐食が散見された。
×:深刻な腐食が発生していた。
(Evaluation)
○: No corrosion was observed.
Δ: Corrosion was observed occasionally.
X: Serious corrosion occurred.
[Al防食性(シャワー法)]
Alを形成したウェハに、50℃に加熱した下記表1に示すフォトレジスト用剥離液を、0.1MPaの圧力で、30分間吹き付けた後のシート抵抗値を測定した。その結果からAlのエッチング量(腐食量)を求め、Alに対する防食性を下記評価基準により評価した。結果を表1に示す。なお、シート抵抗値の測定は、上記Agの防食性試験と同じ測定装置を用いた。
[Al anticorrosion (shower method)]
The sheet resistance value after spraying the photoresist stripping solution shown in Table 1 below heated at 50 ° C. to the Al-formed wafer at a pressure of 0.1 MPa for 30 minutes was measured. From the results, the etching amount (corrosion amount) of Al was obtained, and the anticorrosion properties against Al were evaluated according to the following evaluation criteria. The results are shown in Table 1. The sheet resistance value was measured using the same measuring apparatus as the above-described corrosion prevention test of Ag.
(評価)
○:腐食は全くみられなかった。
△:腐食が散見された。
×:深刻な腐食が発生していた。
(Evaluation)
○: No corrosion was observed.
Δ: Corrosion was observed occasionally.
X: Serious corrosion occurred.
MIPA:モノイソプロパノールアミン
NMEA:N−メチルエタノールアミン
DGA:ジグリコールアミン
BDG:ジエチレングリコールモノブチルエーテル
PG:プロピレングリコール
表1の結果より、実施例1から6の剥離液においては、Alの防食性に優れ、また、フォトレジストの剥離性も優れることが確認された。一方、(C)成分を含有しなかった比較例1、および、(B)成分を含有しなかった比較例2は、充分な剥離性が得られなかった。また、(A)成分を含有しなかった比較例3、防食剤にプロピレングリコールを含有させた比較例4、5はAlの腐食が確認された。比較例の剥離液を用いた場合、剥離性および防食性の両立は得られなかった。 From the results of Table 1, it was confirmed that the stripping solutions of Examples 1 to 6 were excellent in Al anticorrosion properties and excellent in stripping properties of photoresist. On the other hand, Comparative Example 1 that did not contain the component (C) and Comparative Example 2 that did not contain the component (B) did not provide sufficient peelability. Moreover, corrosion of Al was confirmed in the comparative example 3 which did not contain (A) component, and the comparative examples 4 and 5 which made the corrosion inhibitor contain propylene glycol. When the stripping solution of the comparative example was used, it was not possible to achieve both peelability and anticorrosion properties.
Claims (6)
A photoresist film is formed on a substrate on which a metal layer containing aluminum is formed, the photoresist film is exposed and developed, and then the substrate is dry-etched, and the photoresist film residue and etching are performed. A method for treating a substrate, comprising a step of cleaning and removing a residue with the photoresist stripping solution according to claim 1.
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PCT/JP2007/064952 WO2008026408A1 (en) | 2006-08-31 | 2007-07-31 | Photoresist-removing solution, and method for treatment of substrate using the same |
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