TWI610138B - Thinner composition and uses thereof - Google Patents
Thinner composition and uses thereof Download PDFInfo
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- TWI610138B TWI610138B TW103102993A TW103102993A TWI610138B TW I610138 B TWI610138 B TW I610138B TW 103102993 A TW103102993 A TW 103102993A TW 103102993 A TW103102993 A TW 103102993A TW I610138 B TWI610138 B TW I610138B
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- diluent composition
- photosensitive film
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- 239000000203 mixture Substances 0.000 title claims abstract description 113
- 239000003085 diluting agent Substances 0.000 claims abstract description 87
- 239000000758 substrate Substances 0.000 claims abstract description 76
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 63
- 238000009736 wetting Methods 0.000 claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 10
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052814 silicon oxide Inorganic materials 0.000 description 2
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- HVXGFJNIJXPREA-UHFFFAOYSA-N 9h-fluorene;hydrofluoride Chemical compound F.C1=CC=C2CC3=CC=CC=C3C2=C1 HVXGFJNIJXPREA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ALVGSDOIXRPZFH-UHFFFAOYSA-N [(1-diazonioimino-3,4-dioxonaphthalen-2-ylidene)hydrazinylidene]azanide Chemical compound C1=CC=C2C(=N[N+]#N)C(=NN=[N-])C(=O)C(=O)C2=C1 ALVGSDOIXRPZFH-UHFFFAOYSA-N 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001409 amidines Chemical group 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
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- 230000002950 deficient Effects 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-N tert-butyl hydrogen carbonate Chemical group CC(C)(C)OC(O)=O XKXIQBVKMABYQJ-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- 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
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
-
- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
- G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Chemical & Material Sciences (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Materials For Photolithography (AREA)
- Detergent Compositions (AREA)
Abstract
本發明有關一種稀釋劑組成物及其用途。本發明的稀釋劑組成物對各種光阻劑都具有優異的溶解力，且具有最適當的揮發性，因此能夠在短時間內於邊緣球狀物移除製程或類似程序中有效地去除不必要附著的光阻劑，並且可應用於半導體基板的預潤濕製程，以至於能夠有效形成帶有少量光阻劑的感光膜。 The invention relates to a diluent composition and use thereof. The diluent composition of the present invention has excellent dissolving power for various photoresists, and has the most suitable volatility, so it can effectively remove unnecessary in a short time in the edge ball removal process or similar procedures. The attached photoresist can be applied to the pre-wetting process of the semiconductor substrate, so that a photosensitive film with a small amount of photoresist can be effectively formed.
Description
本發明有關一種稀釋劑組成物及其用途，更具體而言，有關一種在半導體製造過程中能夠用於光罩蝕刻製程之各步驟的稀釋劑組成物，以及使用該組成物形成感光膜的方法。 The present invention relates to a diluent composition and use thereof, and more particularly, to a diluent composition that can be used in each step of a photomask etching process in a semiconductor manufacturing process, and a method for forming a photosensitive film using the composition. .
光罩蝕刻(photo lithography)是一種使用光罩將預先設計好的圖案複製到半導體基板上的感光膜，然後依據前述複製的圖案蝕刻前述基板或是下層膜的過程。 Photo lithography is a process of using a photomask to copy a pre-designed pattern onto a photosensitive film on a semiconductor substrate, and then etching the substrate or the underlying film according to the copied pattern.
在光罩蝕刻製程(photolithography process)中，光阻劑被塗布於半導體基板上以形成感光膜。並且，使用曝光設備將感光膜暴露於光線下，以投影出光罩的圖案，之後，進行顯影程序製造出所需形狀的感光膜圖案。接著，使用感光膜圖案蝕刻基板，其後，藉由剝離等等方法將不再需要的感光膜圖案從基板上移除。在此過程中，依據欲形成之圖案的線徑使用諸如G-線(G-line)、I-線(I-line)、氟化氪(KrF)、氟化氬(ArF)、紫外光(ultraviolet rays)、電子束(e-beam)、X光(X-ray)等等各種光源。依據光源的種類、感光膜的性能等等，用於形成感光膜的光阻劑包括各種主要成分的樹脂、光敏劑等等。 In a photolithography process, a photoresist is applied on a semiconductor substrate to form a photosensitive film. In addition, the photosensitive film is exposed to light using an exposure device to project the pattern of the photomask, and then a developing process is performed to produce a desired shape of the photosensitive film pattern. Next, the substrate is etched using the photosensitive film pattern, and thereafter, the unnecessary photosensitive film pattern is removed from the substrate by a method such as peeling. In this process, G-line, I-line, KrF, ArF, ultraviolet light (G-line), I-line ultraviolet rays), e-beam, X-ray, etc. Depending on the type of light source, the performance of the photosensitive film, and the like, the photoresist used to form the photosensitive film includes resins, photosensitizers, and the like with various main components.
同時，在光罩蝕刻製程中，稀釋劑(thinner)組成物指的 是對光阻劑具有溶解力，因而用於移除光阻劑或是作為稀釋劑的物質。用於光阻劑之稀釋劑組成物的溶解力取決於稀釋劑組成物的化學成分以及光阻劑的化學結構。然而，由於前述化學結構會隨光阻劑的種類而大幅改變，因此市售稀釋劑組成物普遍都存有針對各種光阻劑無法具有固定溶解力的問題。具體來說，倘若稀釋劑組成物對於光阻劑的溶解力不足，在用於移除不必要附著於基板之光阻劑的邊緣球狀物移除製程(Edge bead removing,EBR)中，或是在降低光阻劑消耗(Reducing resist consumption,RRC)塗布等等所使用之稀釋劑組成物的預潤濕(pre-wetting)製程中，可能會產生瑕疵，因而可能會導致良率降低。 At the same time, during the photomask etching process, the thinner composition refers to It is a substance that has solubility in photoresist and is therefore used for removing photoresist or as a diluent. The solubility of the diluent composition used in the photoresist depends on the chemical composition of the diluent composition and the chemical structure of the photoresist. However, since the aforementioned chemical structure changes greatly depending on the type of the photoresist, commercially available diluent compositions generally have a problem that the photoresist cannot have a fixed solubility. Specifically, if the solubility of the diluent composition to the photoresist is insufficient, it is used in an edge bead removing (EBR) process for removing photoresist that is not necessarily attached to the substrate, or In the pre-wetting process of a diluent composition used for reducing resist resist (RRC) coating, etc., defects may occur, and thus yield may decrease.
因此，需要發展出一種針對各種光阻劑具有進一步改良之溶解力的稀釋劑組成物。 Therefore, there is a need to develop a diluent composition having further improved solubility for various photoresist agents.
本發明之一目的在於提供一種稀釋劑組成物，其對於各種光阻劑具有進一步改良的溶解力，且可應用於各種形成感光膜的製程中。 It is an object of the present invention to provide a diluent composition which has further improved dissolving power for various photoresist agents and can be applied to various processes for forming a photosensitive film.
本發明之另一目的在於提供一種使用前述稀釋劑組成物形成感光膜的方法。 Another object of the present invention is to provide a method for forming a photosensitive film using the aforementioned diluent composition.
依據本發明一實施例，係提供一種包括有1-甲氧基-2-丙醇醋酸酯(1-methoxy-2-propanol acetate)以及乙二醇丙基醚(ethylene glycol propyl ether)的稀釋劑組成物。 According to an embodiment of the present invention, a system including 1-methoxy-2-propanol acetate and ethylene glycol propyl ether is provided. glycol propyl ether).
前述稀釋劑組成物可包括有20至80wt%的1-甲氧基-2-丙醇醋酸酯，以及20至80wt%的乙二醇丙基醚。 The aforementioned diluent composition may include 20 to 80% by weight of 1-methoxy-2-propanol acetate, and 20 to 80% by weight of ethylene glycol propyl ether.
並且，前述稀釋劑組成物可包括有40至80wt%的1-甲氧基-2-丙醇醋酸酯，以及20至60wt%的乙二醇丙基醚。 In addition, the aforementioned diluent composition may include 40 to 80% by weight of 1-methoxy-2-propanol acetate, and 20 to 60% by weight of ethylene glycol propyl ether.
並且，乙二醇丙基醚可包括乙二醇單丙醚(ethylene glycol monopropyl ether)、乙二醇異丙醚(ethylene glycol isopropyl ether)及其混合物。 Also, the glycol propyl ether may include ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, and a mixture thereof.
前述稀釋劑組成物可進一步包括有一界面活性劑，並且，以100重量份的稀釋劑組成物為基準，前述界面活性劑的含量可為0.001至0.1重量份。 The aforementioned diluent composition may further include a surfactant, and the content of the aforementioned surfactant may be 0.001 to 0.1 part by weight based on 100 parts by weight of the diluent composition.
同時，依據本發明另一實施例，係提供一種感光膜的形成方法，包括有下列步驟：將光阻劑塗布於一半導體基板上；以及將前述稀釋劑組成物施用於前述基板上，以從基板上移除至少一部分的光阻劑。 Meanwhile, according to another embodiment of the present invention, a method for forming a photosensitive film is provided, which includes the following steps: applying a photoresist on a semiconductor substrate; and applying the aforementioned diluent composition to the aforementioned substrate to At least a portion of the photoresist is removed from the substrate.
依據本發明又一實施例，係提供一種感光膜的形成方法，包括有下列步驟：將前述稀釋劑組成物塗布於一半導體基板上以預潤濕(pre-wetting)前述基板；以及將光阻劑塗布於前述預潤濕的基板上。 According to another embodiment of the present invention, a method for forming a photosensitive film is provided, which includes the following steps: coating the aforementioned diluent composition on a semiconductor substrate to pre-wetting the substrate; and photoresist The agent is coated on the pre-wetted substrate.
依據本發明所為的稀釋劑組成物對於各種光阻劑具有優異的溶解力且具有最適當的揮發性，因此能夠在短時間內於邊緣球狀物移除製程等等製程中有效地去除不必要附著的光阻劑，並且可應用於半導體基板的預潤濕製程等等製程，以至於能夠有效形成帶有少量光阻劑的感光膜。 The diluent composition according to the present invention has excellent dissolving power for various photoresist and has the most appropriate volatility, so it can effectively remove unnecessary in a process such as a marginal ball removal process in a short time. The attached photoresist can be applied to processes such as the pre-wetting process of semiconductor substrates, etc., so that a photosensitive film with a small amount of photoresist can be effectively formed.
以下將說明依據本發明之實施例的稀釋劑組成物及其用途。 The diluent composition and its use according to the embodiment of the present invention will be described below.
除非另有明確說明，術語名詞只是用於特定實施例，而非用於限制本發明。 Unless explicitly stated otherwise, the terminology is used only for specific embodiments and is not intended to limit the present invention.
並且，此處使用的單數形式包括複數形式，除非有表示出明確相反的意思。 Also, the singular form used herein includes the plural form unless there is a clear contrary meaning.
並且，此處使用的名詞「包括」係體現特定的特性、區域、整體、步驟、操作、要素或成分，且其並未排除外加其他特定的特性、區域、整體、步驟、操作、要素或成分。 And, the term "comprising" as used herein refers to a specific characteristic, region, whole, step, operation, element, or component, and does not exclude the addition of other specific characteristics, region, whole, step, operation, element, or component .
並且，此處使用的「乙二醇丙基醚」是指乙二醇單丙醚、乙二醇異丙醚或前述之混合物。 The "ethylene glycol propyl ether" used herein refers to ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, or a mixture thereof.
同時，發明人在進行改良光罩蝕刻製程之效率的重複研究過程中已經證實，若將一包括有1-甲氧基-2-丙醇醋酸酯以及乙二醇丙基醚的組成物用作稀釋劑組成物，其具有最適當的揮發性，而且對各種光阻劑還展現出優異的溶解力，因此能夠以更為提高的效率進行邊緣球狀物移除製程、半導體基板的預潤濕製程等等。 At the same time, the inventors have confirmed during repeated studies to improve the efficiency of the photomask etching process that if a composition including 1-methoxy-2-propanol acetate and ethylene glycol propyl ether is used as The diluent composition has the most appropriate volatility and exhibits excellent dissolving power for various photoresists, so it can perform edge ball removal process and pre-wetting of semiconductor substrates with more improved efficiency. Process and so on.
依據本發明一實施例，係提供一種稀釋劑組成物，包括有：1-甲氧基-2-丙醇醋酸酯；以及乙二醇丙基醚。 According to an embodiment of the present invention, a diluent composition is provided, including: 1-methoxy-2-propanol acetate; and ethylene glycol propyl ether.
具體而言，本發明一實施例的稀釋劑組成物不但對於應用於使用諸如氟化氪(KrF)、氟化氬(ArF)等等光源之製程的高極性光阻劑具有優異的溶解力，而且對於應用於使用諸如G-線(G-line)、I-線(I-line)等等光源之製程的光阻劑也具有優異的溶解力，並且，對於用於旋塗式硬光罩(spin on hardmask)製程且在一般有機溶劑中沒有良好溶解性的光阻劑也能夠展現出優異的溶解力。 Specifically, the diluent composition according to an embodiment of the present invention not only has excellent dissolving power for high-polarity photoresist applied to a process using a light source such as krypton fluoride (KrF), argon fluoride (ArF), or the like, It also has excellent dissolving power for photoresist used in processes using light sources such as G-line, I-line, etc., and for spin-on hard masks. (Spin on hardmask) process and photoresist without good solubility in general organic solvents can also show excellent solubility.
因此，在使用光阻劑形成感光膜的製程中，前述稀釋劑組成物可被施用於移除塗布於或是附著於基板邊緣或是背面之光阻劑的邊緣球狀物移除製程，或是可被施用於從基板正面移除不良感光膜的再加工製程。此外，前述稀釋劑組成物可被施用於顯影以及蝕刻後移除感光膜圖案的剝離製程，以及可被施用於降低光阻劑消耗(Reducing resist consumption,RRC)塗布用之稀釋劑組成物的預潤濕(pre-wetting)製程，以形成厚度更均勻的感光膜。 Therefore, in the process of forming a photosensitive film using a photoresist, the aforementioned diluent composition can be applied to an edge ball removal process for removing the photoresist applied to or attached to the edge of the substrate or the back surface, or It is a reprocessing process that can be applied to remove a defective photosensitive film from the front surface of a substrate. In addition, the aforementioned diluent composition can be applied to a stripping process for developing and removing a photosensitive film pattern after etching, and can be applied to a preliminarily thinner composition for reducing resist consumption (RRC) coating. Wetting (pre-wetting) process to form a more uniform photosensitive film.
一般而言，利用旋轉塗布法形成感光膜的程序中，可能會由於離心力使光阻劑凝聚成球形，而於基板邊緣或是背面形成邊緣球狀物，前述邊緣球狀物會成為引發半導體裝置缺陷或是生產設備故障的污染物，且可能成為曝光製程中失焦(defocus)的原因。然而，若是將本發明一實施例的稀釋劑組成物施用於邊緣球狀物移除製程，則 可在不損壞形成於基板正面之感光膜的情形下輕易地移除附著於基板邊緣或是背面的球狀物，因此在基板的邊緣部分可獲得更清晰以及更均勻的感光膜邊界線。 Generally speaking, in the process of forming a photosensitive film by a spin coating method, the photoresist may be aggregated into a spherical shape due to centrifugal force, and edge spheres may be formed on the edge or the back of the substrate. The aforementioned edge spheres may trigger semiconductor devices. Defects or contamination from production equipment failures can be the cause of defocus during the exposure process. However, if the diluent composition according to an embodiment of the present invention is applied to an edge ball removing process, then The balls attached to the edge or the back of the substrate can be easily removed without damaging the photosensitive film formed on the front surface of the substrate, so a clearer and more uniform boundary line of the photosensitive film can be obtained at the edge portion of the substrate.
由於已經用於現存稀釋劑組成物的乳酸乙酯(ethyl lactate)具有高黏度以及相對低的溶解速率，因此其難以充分地改良稀釋劑組成物的清洗性能。此外，乙二醇單乙醚(ethylene glycol monoethyl ether)對於光阻劑具有優異的溶解性，但具有高揮發性以及易燃性，因此當預潤濕光阻劑時，可能會有塗層劣化的問題產生。並且，若是使用由丙酮酸烷酯(alkyl pyruvate)以及丁酮(methyl ethyl ketone)所組成的混合溶劑作為稀釋劑組成物，對於感光膜之重要成分之一，1,2-萘醌二疊氮(1,2-naphtaquinondiazide)光敏劑的溶解度可能會降低。並且，若是使用諸如丙酮酸甲酯(methyl pyruvate)、丙酮酸乙酯(ethyl pyruvate)等等溶劑作為稀釋劑組成物，則在長時間使用後，可能會腐蝕連接於一感光膜旋轉塗布設備的感光廢液儲存桶中的金屬構件。並且，若是使用具有高揮發性之溶劑，諸如丙二醇烷基醚丙酸酯(propylene glycol alkyl ether propionate)以及乙酸丁酯(butyl acetate)等等溶劑的混合溶劑作為稀釋劑組成物來清洗基板背面，基板會被冷卻而增加感光膜的厚度偏差。並且，若是使用具有低揮發性之溶劑，諸如乳酸乙酯(ethyl lactate)以及丁酮(methyl ethyl ketone)的混合溶劑作為稀釋劑組成物，可能會降低基板邊緣的清洗性能。 Since ethyl lactate, which has been used in the existing diluent composition, has high viscosity and a relatively low dissolution rate, it is difficult to sufficiently improve the cleaning performance of the diluent composition. In addition, ethylene glycol monoethyl ether has excellent solubility in photoresist, but has high volatility and flammability. Therefore, when the photoresist is pre-wetted, the coating may deteriorate. Problems arise. In addition, if a mixed solvent composed of alkyl pyruvate and methyl ethyl ketone is used as a diluent composition, 1,2-naphthoquinonediazide is one of the important components of the photosensitive film. (1,2-naphtaquinondiazide) The solubility of the photosensitizer may decrease. In addition, if a solvent such as methyl pyruvate, ethyl pyruvate and the like is used as a diluent composition, after a long period of use, the solvent connected to a photosensitive film spin coating device may be corroded. Metal components in a photosensitive waste liquid storage tank. In addition, if a highly volatile solvent, such as a mixed solvent of propylene glycol alkyl ether propionate and butyl acetate, is used as a diluent composition to clean the back of the substrate, The substrate is cooled to increase the thickness deviation of the photosensitive film. In addition, if a solvent with low volatility, such as a mixed solvent of ethyl lactate and methyl ethyl ketone, is used as the diluent composition, the cleaning performance of the substrate edge may be reduced.
相反地，包含在本發明一實施例之稀釋劑組成物中的1-甲氧基-2-丙醇醋酸酯(1-methoxy-2-propanol acetate)對於各種光阻劑具 有優異的溶解力，且同時具有最適當的揮發性、黏度以及表面張力。 In contrast, the 1-methoxy-2-propanol acetate included in the diluent composition of an embodiment of the present invention is useful for various photoresist agents. Has excellent dissolving power, and at the same time has the most appropriate volatility, viscosity and surface tension.
依據一範例，稀釋劑組成物中可包含有20至80wt%的1-甲氧基-2-丙醇醋酸酯。依據另一範例，1-甲氧基-2-丙醇醋酸酯的含量可為40至80wt%。依據再一範例，1-甲氧基-2-丙醇醋酸酯的含量可為40至70wt%。 According to an example, the diluent composition may include 20 to 80% by weight of 1-methoxy-2-propanol acetate. According to another example, the content of 1-methoxy-2-propanol acetate may be 40 to 80% by weight. According to yet another example, the content of 1-methoxy-2-propanol acetate may be 40 to 70% by weight.
換句話說，稀釋劑組成物中之1-甲氧基-2-丙醇醋酸酯的含量最好為20wt%或更多，以對具有高極性的光阻劑以及用於旋塗式硬光罩製程的光阻劑展現出優異的溶解力。然而，倘若1-甲氧基-2-丙醇醋酸酯的含量過多，則稀釋劑組成物的揮發性會提高而產生感光膜的厚度偏差或是在預潤濕後產生邊緣龜裂。因此，為了避免這些現象，前述稀釋劑組成物中之1-甲氧基-2-丙醇醋酸酯的含量最好為80wt%或更低。 In other words, the content of 1-methoxy-2-propanol acetate in the diluent composition is preferably 20% by weight or more for the photoresist with high polarity and for spin-on hard light. The photoresist of the cap process exhibits excellent dissolving power. However, if the content of 1-methoxy-2-propanol acetate is too large, the volatility of the diluent composition will increase, and thickness deviation of the photosensitive film may occur, or edge cracking may occur after pre-wetting. Therefore, in order to avoid these phenomena, the content of 1-methoxy-2-propanol acetate in the aforementioned diluent composition is preferably 80% by weight or less.
同時，相較於其他溶劑，包含在本發明一實施例之稀釋劑組成物中的乙二醇丙基醚(ethylene glycol propyl ether)對於光阻劑的光敏成分可展現出優異的溶解力，具體而言，乙二醇丙基醚對於普遍包含在用於旋塗式硬光罩製程之光阻劑中的C-硬光罩(C-Hardmask)結構的極難溶解聚合物，可展現出極佳的溶解力。其中，乙二醇丙基醚包括乙二醇單丙醚、乙二醇異丙醚及其混合物，並且，前述化合物中的每一個或是前述化合物的混合物可展現出實質上相等的效果。在混合物的例子中，乙二醇單丙醚與乙二醇異丙醚的混合比例並沒有特定限制。 At the same time, compared with other solvents, ethylene glycol propyl ether contained in the diluent composition of an embodiment of the present invention can exhibit excellent dissolving power for the photosensitive components of the photoresist. Specifically, In terms of glycol propyl ether, it is extremely difficult to dissolve polymers with a C-Hardmask structure that is commonly contained in photoresist used in spin-on hard mask processes, and it can show extremely Good solubility. Among them, ethylene glycol propyl ether includes ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, and mixtures thereof, and each of the aforementioned compounds or a mixture of the aforementioned compounds can exhibit substantially equal effects. In the example of the mixture, the mixing ratio of ethylene glycol monopropyl ether and ethylene glycol isopropyl ether is not particularly limited.
並且，依據一範例，稀釋劑組成物中可包含有20至80 wt%的乙二醇丙基醚。依據另一範例，乙二醇丙基醚的含量可為20至60wt%。依據再一範例，乙二醇丙基醚的含量可為30至60wt%。 And, according to an example, the diluent composition may include 20 to 80 wt% ethylene glycol propyl ether. According to another example, the content of ethylene glycol propyl ether may be 20 to 60% by weight. According to yet another example, the content of glycol propyl ether may be 30 to 60% by weight.
換句話說，為了獲得對光阻劑之光敏成分以及芘結構之聚合物的溶解力改良效果，稀釋劑組成物中之乙二醇丙基醚的含量最好為20wt%或更多。然而，倘若乙二醇丙基醚的含量過多，則稀釋劑組成物的黏度會增加而產生感光膜的厚度偏差或是在預潤濕後產生邊緣龜裂。因此，為了避免這些現象，前述稀釋劑組成物中之乙二醇丙基醚的含量最好為80wt%或更低。 In other words, in order to obtain the effect of improving the solubility of the photosensitive component of the photoresist and the polymer of the amidine structure, the content of the glycol propyl ether in the diluent composition is preferably 20% by weight or more. However, if the content of ethylene glycol propyl ether is too large, the viscosity of the diluent composition will increase to cause a thickness deviation of the photosensitive film or cause edge cracking after pre-wetting. Therefore, in order to avoid these phenomena, the content of the glycol propyl ether in the aforementioned diluent composition is preferably 80% by weight or less.
若稀釋劑組成物的揮發性過高，當稀釋劑組成物塗布時，基板會迅速地冷卻且感光膜的厚度偏差會顯著地提高。並且，若稀釋劑組成物的揮發性過低，當預潤濕時，在基板上會留下過量的稀釋劑組成物，以致感光膜可能會溶解或是引發諸如感光膜變形的缺陷，而且在移除邊緣球狀物之後，稀釋劑組成物可能會殘留在基板上，而在後續製程中成為污染物。 If the volatility of the diluent composition is too high, when the diluent composition is applied, the substrate is rapidly cooled and the thickness deviation of the photosensitive film is significantly increased. In addition, if the volatility of the thinner composition is too low, when pre-wetting, an excessive amount of the thinner composition will be left on the substrate, so that the photosensitive film may be dissolved or cause defects such as deformation of the photosensitive film, and After the edge ball is removed, the diluent composition may remain on the substrate and become a contaminant in subsequent processes.
此外，依據該實施例之稀釋劑組成物可進一步包含一界面活性劑。考慮到感光膜形成方法的特性，前述界面活性劑最好可為非離子型界面活性劑。關於前述非離子型界面活性劑，可使用本技術領域中常使用的非離子型界面活性劑，且其結構並無特定限制。 In addition, the diluent composition according to this embodiment may further include a surfactant. Considering the characteristics of the photosensitive film forming method, the aforementioned surfactant may preferably be a non-ionic surfactant. Regarding the aforementioned nonionic surfactant, a nonionic surfactant commonly used in the technical field can be used, and its structure is not particularly limited.
以100重量份的稀釋劑組成物為基準，前述界面活性劑的含量可為0.001至0.1重量份。換句話說，為了在邊緣球狀物移除製程中獲得更優異的輪廓，以100重量份的稀釋劑組成物為基準，前述界面活性劑的含量為0.001重量份或更多是較為有利的。然而，倘若界面活 性劑的含量過多，稀釋劑組成物中可能會嚴重地產生泡沫，因而當稀釋劑組成物使用時，可能會引起液體量感應器的故障。因此，為了避免此問題，以100重量份的稀釋劑組成物為基準，前述界面活性劑的含量最好為0.1重量份或更少。 The content of the aforementioned surfactant may be 0.001 to 0.1 parts by weight based on 100 parts by weight of the diluent composition. In other words, in order to obtain a more excellent profile in the edge ball removal process, it is advantageous that the content of the aforementioned surfactant is 0.001 part by weight or more based on 100 parts by weight of the diluent composition. However, if the interface is active Too much content of the sexual agent may cause serious foaming in the diluent composition. Therefore, when the diluent composition is used, the liquid amount sensor may malfunction. Therefore, in order to avoid this problem, the content of the aforementioned surfactant is preferably 0.1 part by weight or less based on 100 parts by weight of the diluent composition.
如前所述，本發明之稀釋劑組成物具有最適當的揮發性，且同時對於各種光阻劑(特別是用於氟化氪(KrF)、氟化氬(ArF)製程之具有高極性的光阻劑，以及用於旋塗式硬光罩製程之在有機溶劑中具有不良溶解性的光阻劑)可展現出更為改善的溶解力。因此，前述稀釋劑組成物可應用於邊緣球狀物移除製程(Edge bead removing,EBR)、用以降低光阻劑消耗(Reducing resist consumption,RRC)塗布之稀釋劑組成物的預潤濕(pre-wetting)製程中，以改善製程效率。 As mentioned above, the diluent composition of the present invention has the most appropriate volatility, and at the same time, it is highly polar for various photoresists (especially those used in the process of KrF and ArF). Photoresist, and photoresist with poor solubility in organic solvents used in spin-on hard mask manufacturing processes) can exhibit more improved dissolving power. Therefore, the aforementioned diluent composition can be applied to the edge bead removing (EBR) process, and the pre-wetting of the diluent composition applied to reduce the resist resist consumption (RRC) ( pre-wetting) process to improve process efficiency.
同時，依據本發明另一實施例，係提供一種感光膜的形成方法，包括有將前述稀釋劑組成物塗布於一半導體基板上以預潤濕(pre-wetting)前述基板；以及將光阻劑塗布於前述預潤濕的基板上。 At the same time, according to another embodiment of the present invention, a method for forming a photosensitive film is provided, which comprises coating the aforementioned diluent composition on a semiconductor substrate to pre-wetting the substrate; and a photoresist Coated on the pre-wetted substrate.
並且，依據本發明又一實施例，係提供一種感光膜的形成方法，包括有將光阻劑塗布於一半導體基板上；以及將前述稀釋劑組成物施用於前述基板上，以從基板上移除至少一部分的光阻劑。 In addition, according to another embodiment of the present invention, a method for forming a photosensitive film is provided, which includes coating a photoresist on a semiconductor substrate; and applying the diluent composition to the substrate to remove the substrate from the substrate. Remove at least a portion of the photoresist.
在感光膜的形成方法中，該半導體基板可為一用於製造諸如記憶體裝置、積體電路裝置、液晶顯示裝置等等電子裝置的基板。各種構成前述電子裝置的結構，舉例來說，絕緣膜、導電膜、佈線(wirings)、穿孔、閘極(gate)等等可形成於前述基板上，並且，由於這些結構，前述基板頂面可能存有不同的高度。 In the method for forming a photosensitive film, the semiconductor substrate may be a substrate for manufacturing electronic devices such as a memory device, an integrated circuit device, a liquid crystal display device, and the like. Various structures constituting the aforementioned electronic device, for example, insulating films, conductive films, wirings, perforations, gates, etc. may be formed on the aforementioned substrate, and due to these structures, the top surface of the aforementioned substrate may be There are different heights.
前述預潤濕製程是一種將如上所述之稀釋劑組成物塗布於一待形成一感光膜之半導體基板上的製程，藉以在塗布光阻劑之前改善基板的濕潤性。具體而言，由於本發明之稀釋劑組成物對於各種光阻劑展現出更為改善的溶解力，因此其可經由前述預潤濕製程而形成具有均勻厚度之帶有少量光阻劑的感光膜。換句話說，若是使用如上所述之稀釋劑組成物進行預潤濕製程，透過使用相對較少量的光阻劑，就可形成厚度又薄又均勻的膜。此外，基板邊緣上的感光膜缺陷塗層可以被降低，可能存在於基板上的高度差異也可輕易地被克服，以降低感光膜的厚度偏差。 The aforementioned pre-wetting process is a process of coating the diluent composition as described above on a semiconductor substrate to be formed with a photosensitive film, so as to improve the wettability of the substrate before coating the photoresist. Specifically, since the diluent composition of the present invention exhibits more improved dissolving power for various photoresists, it can form a photosensitive film with a small amount of photoresist having a uniform thickness through the aforementioned pre-wetting process. . In other words, if the pre-wetting process is performed using the diluent composition as described above, by using a relatively small amount of a photoresist, a thin and uniform film can be formed. In addition, the photosensitive film defect coating on the edge of the substrate can be reduced, and the height difference that may exist on the substrate can also be easily overcome to reduce the thickness deviation of the photosensitive film.
前述預潤濕製程可藉由一般的旋轉塗布法來進行，舉例來說，藉由將稀釋劑組成物施用於基板上，之後旋轉該基板以將稀釋劑組成物塗布於該基板的正面，或是藉由將稀釋劑組成物施用於一旋轉基板，以將稀釋劑組成物塗布於該基板的正面。 The foregoing pre-wetting process may be performed by a general spin coating method, for example, by applying a diluent composition to a substrate, and then rotating the substrate to apply the diluent composition to the front surface of the substrate, or The thinner composition is applied to a rotating substrate to apply the thinner composition to the front surface of the substrate.
此外，在感光膜的形成方法中，光阻劑取決於欲形成之圖案的線徑以及使用之光源的種類等等，並且，其結構並無特定限制。作為參考示例，前述光阻劑可包括用於I-線之包含有酚醛清漆樹脂(novolac resin)的光阻劑；用於氟化氪(KrF)之包含有聚羥基苯乙烯(polyhydroxystyrene)的光阻劑，前述聚羥基苯乙烯中之羥基的氫係部分被縮醛基(acetal group)封端；用於氟化氪(KrF)之包含有聚羥基苯乙烯的光阻劑，前述聚羥基苯乙烯中之羥基的氫係部分被三級-丁基碳酸酯基(tert-butylcarbonate group)封端；用於氟化氬(ArF)之包含有甲基丙烯酸酯樹脂(methacrylate resin)的光阻劑；用於氟化氪(KrF)之包含有三 嗪系樹脂(triazine resin)的底部抗反射塗層；用於氟化氬(ArF)之包含有酯系樹脂(ester resin)的底部抗反射塗層等等。並且，作為參考示例，前述用於I-線之光阻劑可包括有酚醛清漆樹脂以及作為光敏劑的2,4-二硝苯醌(2,4-dinitroquinone)。前述用於氟化氪(KrF)之光阻劑可包括有羥基苯乙烯以及作為光敏劑的三苯基鋶鹽(triphenylsulfonium salt)，前述聚羥基苯乙烯中之羥基的氫係部分被縮醛基或是三級-丁基碳酸酯基封端。前述用於氟化氬(ArF)之光阻劑可包括有以金剛烷基(adamantyl group)及/或4-氧雜三環(4.2.1.0(3,7))-5-壬酮(4-oxa-tricyclo(4.2.1.0(3,7))nonan-5-one)封端的聚甲基丙烯酸酯以及作為光敏劑的三苯基鋶鹽。 In addition, in the method of forming the photosensitive film, the photoresist depends on the line diameter of the pattern to be formed, the type of light source used, and the like, and its structure is not particularly limited. As a reference example, the aforementioned photoresist may include a photoresist containing novolac resin for I-line; a light containing polyhydroxystyrene for fluorinated fluoride (KrF) A resist, the hydrogen-based portion of the hydroxyl group in the aforementioned polyhydroxystyrene is capped with an acetal group; a photoresist containing polyhydroxystyrene for fluorene fluoride (KrF), the aforementioned polyhydroxybenzene Hydrogen part of hydroxyl group in ethylene is terminated by tert-butylcarbonate group; photoresist containing methacrylate resin for argon fluoride (ArF) ; Contains three for KrF Bottom anti-reflective coating of triazine resin; bottom anti-reflective coating containing ester resin for argon fluoride (ArF), etc. And, as a reference example, the aforementioned photoresist for I-line may include a novolac resin and 2,4-dinitroquinone as a photosensitizer. The aforementioned photoresist for fluorinated fluorene (KrF) may include hydroxystyrene and triphenylsulfonium salt as a photosensitizer. The hydrogen-based portion of the hydroxyl group in the polyhydroxystyrene is acetalized. Or tertiary-butyl carbonate-terminated. The aforementioned photoresist for argon fluoride (ArF) may include adamantyl group and / or 4-oxatricyclo (4.2.1.0 (3,7))-5-nonanone (4 -oxa-tricyclo (4.2.1.0 (3,7)) nonan-5-one) terminated polymethacrylate and triphenylphosphonium salt as a photosensitizer.
此外，將光阻劑塗布於預潤濕之基板上的步驟可藉由旋轉塗布法來進行。如果利用旋轉塗布法塗布光阻劑，會由於離心力使光阻劑凝聚成球形，而於基板邊緣或是背面形成邊緣球狀物。前述邊緣球狀物會成為引發電子裝置缺陷或是生產設備故障的污染物，且可能成為曝光製程中失焦的原因。 In addition, the step of applying the photoresist on the pre-wetted substrate can be performed by a spin coating method. If the photoresist is applied by a spin coating method, the photoresist will be aggregated into a spherical shape due to centrifugal force, and an edge ball is formed on the edge or the back of the substrate. The aforementioned edge spheroids may be a pollutant that causes defects in electronic devices or production equipment failures, and may be a cause of defocusing during the exposure process.
因此，本發明的稀釋劑組成物可被用來移除基板上至少一部分的光阻劑，例如附著於基板邊緣或是背面的光阻劑。前述移除可在旋轉基板時利用稀釋劑組成物的加壓噴霧予以進行。如前所述，由於本發明之稀釋劑組成物對於各種光阻劑具有優異的溶解力以及最適當的性質，諸如揮發性、黏度等等，因此在清除感光膜的邊界線時，前述稀釋劑組成物可精確地只移除邊緣球狀物，並可在短時間內有效率地進行製程。 Therefore, the diluent composition of the present invention can be used to remove at least a portion of the photoresist on the substrate, such as a photoresist attached to the edge or the back of the substrate. The aforementioned removal can be performed by using a pressure spray of the diluent composition when the substrate is rotated. As mentioned above, since the diluent composition of the present invention has excellent dissolving power and the most appropriate properties for various photoresist, such as volatility, viscosity, etc., when the boundary line of the photosensitive film is removed, the aforementioned diluent The composition can precisely remove only the edge spheres, and can efficiently process in a short time.
在移除至少一部分光阻劑的步驟(邊緣球狀物移除製程)中所使用的稀釋劑組成物，與如上所述之預潤濕製程所使用的稀釋劑組成物可以相同或是不同。換句話說，依據各個製程的情況以及所需性質等等，可以使用具有不同組分的稀釋劑組成物。然而，由於本發明的稀釋劑組成物可滿足適用於邊緣球狀物移除製程以及預潤濕製程的性質，因此在改善整體製程效率方面，最好使用具有同等範圍之組分的稀釋劑組成物。 The diluent composition used in the step of removing at least a portion of the photoresist (edge ball removal process) may be the same as or different from the diluent composition used in the pre-wetting process as described above. In other words, a diluent composition having different components may be used depending on the conditions of each process and the required properties and so on. However, since the diluent composition of the present invention can satisfy the properties applicable to the edge ball removal process and the pre-wetting process, it is better to use a diluent composition having components in the same range in terms of improving the overall process efficiency Thing.
移除附著於基板邊緣或是背面的邊緣球狀物後，可透過軟烘烤製程形成感光膜，並且，在使用缺陷檢測設備確認感光膜上有無產生缺陷後，就可透過曝光以及顯影製程形成感光圖案。若是感光膜具有諸如裂痕(tearing)、尾渣(tailing)、厚度偏差等等的缺陷，則藉由進行再加工(rework)製程移除形成於基板正面的感光膜，並且，在此製程中，也可使用本發明的稀釋劑組成物。 After removing the edge balls attached to the edge of the substrate or the back, a photosensitive film can be formed through the soft baking process. After confirming whether defects occur on the photosensitive film using a defect detection device, it can be formed through exposure and development processes. Photographic pattern. If the photosensitive film has defects such as tearing, tailing, thickness deviation, etc., the photosensitive film formed on the front surface of the substrate is removed by a rework process, and, in this process, The diluent composition of the present invention can also be used.
以下，透過較佳實施例以有助於理解本發明。然而，這些實施例僅用於說明本發明，本發明並不受限於此。 In the following, preferred embodiments are provided to help understand the present invention. However, these examples are only for illustrating the present invention, and the present invention is not limited thereto.
範例1Example 1
將80wt%的1-甲氧基-2-丙醇醋酸酯以及20wt%的乙二醇單丙醚導入一配備有攪拌器的混合容室中，前述混合物於室溫下攪拌約50分鐘以製備稀釋劑組成物。 80 wt% of 1-methoxy-2-propanol acetate and 20 wt% of ethylene glycol monopropyl ether were introduced into a mixing chamber equipped with a stirrer, and the foregoing mixture was stirred at room temperature for about 50 minutes to prepare Thinner composition.
範例2至7以及比較範例1至10Examples 2 to 7 and Comparative Examples 1 to 10
以與範例1相同的方式製備稀釋劑組成物，除了下表1所示成分係以相對應的含量(wt%；然而，界面活性劑的含量單位為 重量份，以100重量份的剩餘成分為基準)予以混合之外。 A diluent composition was prepared in the same manner as in Example 1, except that the ingredients shown in Table 1 below are in the corresponding content (wt%; however, the unit of content of the surfactant is Parts by weight, based on 100 parts by weight of the remaining ingredients).
表1中的成分A到G係如下所示。 The components A to G in Table 1 are shown below.
[A]1-甲氧基-2-丙醇醋酸酯(1-methoxy-2-propanol acetate) [A] 1-methoxy-2-propanol acetate
[B]乙二醇單丙醚(ethylene glycol monopropyl ether) [B] ethylene glycol monopropyl ether
[C]2-羥基異丁酸甲酯(methyl 2-hydroxyisobutyrate) [C] methyl 2-hydroxyisobutyrate
[D]醋酸正丁酯(n-buthyl acetate) [D] n-buthyl acetate
[E]γ-丁內酯(gamma-butyrolactone) [E] gamma-butyrolactone
[F]3-乙氧基丙酸乙酯(ethyl 3-ethoxypropionate) [F] ethyl 3-ethoxypropionate
[G]非離子型界面活性劑(產品名：BYK-Series，製造商ALTANA) [G] Non-ionic surfactant (product name: BYK-Series, manufacturer ALTANA)
實驗例1Experimental example 1
(依據感光膜種類之邊緣球狀物移除性能的評估) (Evaluation of the edge ball removal performance based on the type of photosensitive film)
將8吋氧化矽基板浸漬於兩個過氧化氫/硫酸混合物浴中各5分鐘，之後以超純水清洗。接著，在旋轉乾燥器(spin drier)中旋轉乾燥該基板，其後，將範例1的稀釋劑組成物旋轉塗布(約1500至2500rpm)於基板，以進行降低光阻劑消耗(RRC)塗布的預潤濕製程。接著，在預潤濕的基板上，將下表2所述的各個光阻劑旋轉塗布(在約300rpm旋轉下約3秒，之後，在約1000至2000rpm旋轉下約20至30秒，以控制成預定厚度)於基板，以形成具有相應厚度的感光膜。此外，使用範例1至7以及比較範例1至10的稀釋劑組成物進行用以移除不必要附著於基板邊緣部分的邊緣球狀物試驗。 An 8-inch silicon oxide substrate was immersed in two hydrogen peroxide / sulfuric acid mixture baths for 5 minutes each, and then washed with ultrapure water. Next, the substrate is spin-dried in a spin drier, and then the thinner composition of Example 1 is spin-coated (about 1500 to 2500 rpm) on the substrate to reduce the photoresist consumption (RRC) coating. Pre-wetting process. Next, on the pre-wet substrate, each photoresist described in Table 2 below was spin-coated (about 3 seconds at about 300 rpm rotation, and then about 20 to 30 seconds at about 1000 to 2000 rpm rotation to control Into a predetermined thickness) on the substrate to form a photosensitive film having a corresponding thickness. In addition, the thinner compositions of Examples 1 to 7 and Comparative Examples 1 to 10 were used to perform edge ball tests to remove unnecessary adherence to the edge portion of the substrate.
在試驗中，各稀釋劑組成物係由配備有壓力表的加壓容器(增壓壓力約1.0kgf)予以供應，並藉由EBR噴嘴噴出(組成物的流速為10至20cc/分鐘)，並且，如下表3所述，組成物的噴灑時間由基板的轉速予以控制。 In the test, each diluent composition was supplied from a pressurized container (pressurized pressure of about 1.0 kgf) equipped with a pressure gauge and ejected through an EBR nozzle (the composition flow rate was 10 to 20 cc / minute), and As described in Table 3 below, the spray time of the composition is controlled by the rotation speed of the substrate.
此外，評估邊緣球狀物移除效率的結果顯示於表4以及表5。在下表4與表5中，「◎」表示邊緣球狀物移除後，EBR線均勻性(EBR line uniformity)是均勻且恆定的；「○」表示邊緣球狀物移除後，EBR線均勻性有80%或更高符合要求；「△」表示邊緣球狀物移除後，EBR線均勻性有50%或更高但低於80%符合要求；「×」表示邊緣球狀物移除後，EBR線均勻性有20%或更高但低於50%符合要求，且在邊緣處出現尾渣(tailing)。 In addition, the results of evaluating the removal efficiency of the edge spheres are shown in Tables 4 and 5. In the following Tables 4 and 5, "◎" indicates that the EBR line uniformity is uniform and constant after the edge ball is removed; "○" indicates that the EBR line is uniform after the edge ball is removed 80% or higher meets the requirements; "△" indicates that after the edge ball is removed, the EBR line uniformity is 50% or higher but less than 80% meets the requirements; "×" indicates that the edge ball is removed Later, EBR line uniformity of 20% or more but less than 50% meets the requirements, and tailing occurs at the edges.
[表2]
實驗例2Experimental example 2
(光阻劑塗布均勻性的評估) (Evaluation of photoresist coating uniformity)
以下列方式評估感光膜是否均勻地塗布於基板的正面。 It was evaluated in the following manner whether the photosensitive film was uniformly coated on the front surface of the substrate.
將8吋氧化矽基板浸漬於兩個過氧化氫/硫酸混合物浴中各5分鐘，之後以超純水清洗。接著，在旋轉乾燥器(spin drier)中旋轉乾燥該基板，其後，將範例1至7以及比較範例1至10的稀釋劑組成物旋轉塗布(約1500至2500rpm)於基板，以進行降低光阻劑消耗(RRC)塗布的預潤濕製程。此時，各稀釋劑組成物係由配備有壓力表的加壓容器(增壓壓力約1.0kgf)予以供應，並藉由噴嘴噴出(組成物的流速為10至20cc/分鐘)，並且，如下表6所述，組成物的噴灑時間由基板的轉速予以控制。 An 8-inch silicon oxide substrate was immersed in two hydrogen peroxide / sulfuric acid mixture baths for 5 minutes each, and then washed with ultrapure water. Next, the substrate was spin-dried in a spin drier, and then the thinner compositions of Examples 1 to 7 and Comparative Examples 1 to 10 were spin-coated (about 1500 to 2500 rpm) on the substrate to reduce light. Resistor Consumption (RRC) coated pre-wetting process. At this time, each diluent composition is supplied from a pressurized container (pressurized pressure of about 1.0 kgf) equipped with a pressure gauge, and is ejected through a nozzle (the composition flow rate is 10 to 20 cc / minute), and is as follows As shown in Table 6, the spray time of the composition was controlled by the rotation speed of the substrate.
接著，在預潤濕的基板上，將表2所述的各個光阻劑旋轉塗布(在約300rpm旋轉下約3秒，之後，在約1000至2000rpm旋轉下約20至30秒，以控制成預定厚度)於基板，以形成具有相應厚度的感光膜。 Next, each photoresist described in Table 2 was spin-coated on the pre-moistened substrate (about 3 seconds at about 300 rpm rotation, and then about 20 to 30 seconds at about 1000 to 2000 rpm rotation to control the (Predetermined thickness) on the substrate to form a photosensitive film having a corresponding thickness.
此外，評估各感光膜塗布均勻性的結果顯示於下表7以及表8。在表7與表8中，「○」表示感光膜的塗布均勻性是均勻且恆定的；「△」表示邊緣球狀物移除後，EBR線均勻性有90%或更高符合要求；「×」表示感光膜的邊緣部分出現塗布缺陷。 The results of evaluating the coating uniformity of each photosensitive film are shown in Tables 7 and 8 below. In Tables 7 and 8, "○" indicates that the coating uniformity of the photosensitive film is uniform and constant; "△" indicates that 90% or more of the EBR line uniformity meets the requirements after the edge ball is removed; " “×” indicates that coating defects occurred at the edge portion of the photosensitive film.
[表6]
由實驗例1以及實驗例2所示結果證實，相較於比較範例的稀釋劑組成物，範例1至7的稀釋劑組成物對於各種光阻劑展現出優異的溶解力，使得邊緣球狀物移除製程以及基板的預潤濕製程能夠更有效率地進行。 From the results shown in Experimental Example 1 and Experimental Example 2, it was confirmed that the diluent compositions of Examples 1 to 7 exhibited superior dissolving power to various photoresists compared to the diluent composition of the comparative example, making the edges spherical The removal process and the substrate pre-wetting process can be performed more efficiently.
具體而言，實驗結果證實，相較於比較範例的稀釋劑組 成物，範例1至7的稀釋劑組成物對於I-線用光阻劑(PR1以及PR2)具有溶解力，對於氟化氪(KrF)及氟化氬(ArF)用之高極性光阻劑(PR3至PR6)具有溶解力，對於旋塗式硬光罩用之難溶光阻劑(PR7以及PR8)具有優異的溶解力。 Specifically, the experimental results confirm that compared to the diluent group of the comparative example The product, the diluent composition of Examples 1 to 7 has a dissolving power for the photoresist for I-line (PR1 and PR2), and a high-polarity photoresist for krypton fluoride (KrF) and argon fluoride (ArF) (PR3 to PR6) have dissolving power, and have excellent dissolving power for hard-to-dissolve photoresist (PR7 and PR8) for spin-on hard mask.
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