WO1992005474A1 - Top coat for acid catalyzed resists - Google Patents
Top coat for acid catalyzed resists Download PDFInfo
- Publication number
- WO1992005474A1 WO1992005474A1 PCT/US1990/007618 US9007618W WO9205474A1 WO 1992005474 A1 WO1992005474 A1 WO 1992005474A1 US 9007618 W US9007618 W US 9007618W WO 9205474 A1 WO9205474 A1 WO 9205474A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- resist
- polymeric film
- film forming
- acid catalyzed
- Prior art date
Links
Classifications
-
- 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
- G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
Definitions
- the invention relates to acid catalyzed resist formulations. More particularly, the present invention is concerned with a protective topcoat material for use as an overcoating film for acid catalyzed resist compositions.
- U.S. Patent No. 3,753,715 discloses the use of certain water soluble macromolecular organic polymers in controlling oxygen diffusion in photopolymerizable copying process.
- the barrier materials include polyvinyl alcohol and its partial esters, and partial acetals, as well as other natural and synthetic materials of higher molecular weights such as gelatin, gum arabi ⁇ , copolymer of methylvinyl ether and maleic anhydride, polyvinyl pyrrolidones, and water soluble polymers of ethylene oxide with molecular weights in the range from 100,000 to 3,000,000. Wetting agents in relatively small quantities have been included in such aqueous coating solutions.
- the drawbacks of such barrier materials include the necessity for certain minimum drying times to form homogeneous coatings and the impermeability of the layers to light that an effective oxygen transfer cannot be maintained.
- U.S. Patent No. 3,652,273 discloses the use of polyvinyl butyral as a topcoat for photoresist. This topcoat provides protection against oxygen and high humidity and results in less scumming of and pinholing in the hydrophobic resist. The topcoat film is soluble in the developer and does not interfere with imaging.
- U.S. Patent No. 4,756,988 discloses the use of a non-photosensitive crosslinkable adhesive layer to provide performance improvements in the areas of resistance to crazing of the film during storage, photosensitivity in that the photospeed is increased to make the films more processable, enabling the fabrication of photoresists without using alkoxysilane adhesion promoters, and improving thermal dimensional stability of the film during
- the topcoat compositions include terpolymers of ethylacrylate, methylacrylate and acrylic acid.
- IBM Technical Disclosure Bulletin, Vol. 12, No. 9, pp. 1418-19, discloses the use of azidosulfono-stilbene films as a topcoat to prevent oxygen diffusion into photoresist films to consume sensitizer radicals.
- the polyvinyl acetate impedes oxygen diffusion.
- Japanese Patent Publication 58-178340 is directed to a process for forming images by exposing a photosensitive material prepared by coating a substrate with a photosensitive layer and a protective layer of polyvinyl alcohol which is water insoluble but is water swellable after exposure to light, removing the polyvinyl alcohol layer with water and developing the photosensitive layer.
- European Patent Application 0160468 is directed to the use of a number of materials including polyethylene oxide as a protective topcoat against ozone generated in a flexographic printing process.
- the use of this topcoat leads to the improved adhesion of inks to corona treated cardboard.
- Japanese Patent Publication No. 60 200249 relates to the use of a polyvinyl alcohol as an antisticking layer between a topcoat layer and a photosensitive layer on a substrate.
- p 6521 discloses the use of polyvinyl alcohol as a top depth-of-focus enhancement layer owing to the optical properties of the polyvinyl alcohol film. No suggestion of barrier properties is made.
- Acid catalyzed resists are based upon mechanisms which involve the radiation induced generation of a Lewis or Bronsted acid from acid precursors such as sulfonates and triflates of onium salts and oxime and dicarboximide derivatives.
- the radiation induced formation of acid catalyzes the decarbonylation of the resist such as the poly-p-tertbutyloxycarbonyloxystyrene compositions as set forth in U.S. Patent No. 4,491,628.
- Other acid catalyzed reactions include the cleaving of diacetals of novolaks and the acid catalyzed crosslinking of epoxy and melamine based resists.
- acid catalyzed image amplified resist are very reactive compositions, i.e., they have a high photospeed, they also exhibit an extreme sensitivity to environmental chemicals present in the process areas, even when they are present only at the p.p.b. level. If wafers having an imaged and exposed acid catalyzed resist such as poly-p-tertbutyloxycarbonyloxystyrene are left open to process air, they suffer from profile deterioration and eventually no discernible images will be formed. The desensitization of the resist is believed to be due to the poisoning of the acid generator and the acids formed by the absorption of vapors of organic amines and/or inorganic bases.
- compositions were exposed to ppb levels of organic vapors of N-methyl-2-pyrrolidone(NMP) , ammonia, pyridine and triethylamine and rapid desensitization of the resists was noted. Since these resists are sensitive to organic vapors at the ppb levels, it is not practical or economical to remove all of these vapors from a manufacturing process area or from inside of those tools, designed to operate at atmospheric conditions. Additionally, a wafer may be exposed to process air for up to 15 minutes inside a deep UV stepper or scanning tool. Different portions of large wafers, e.g., 200 mm diameter wafers may experience different periods of exposure to process air. Desensitization may cause certain portions of the wafer to be undeveloped or have localized distorted images.
- the barrier layer has also been found to increase the sensitivity of coated acid sensitized resists when such resists are used in electron beam tools. Uncoated resists tend to experience an outgassing of acid and acid-degraded fragments due to their partial pressures.
- the use of the barrier inhibits the removal of acid from the resist film and, therefore, enhances the effect of the acid in promoting the patterned exposure.
- Barrier topcoats have been previously used to protect free radical based resist systems which are oxygen sensitive. These include a 25 um Mylar film on DuPont Riston acrylate crosslinking resist and the use of 2 um film of polyvinylalcohol on top of a free radical polyolefin sulfone-novolak based x-ray resist. For such uses, films of polyvinylalcohol thinner than about 0.5um does not function as an -6- effective oxygen barrier topcoat. The thicker barriers are thought to prevent oxygen from diffusing into the exposed resist films and consuming some or all of the radical initiators. Topcoats which
- a protective topcoat has to be thin and permeable in order to allow the gaseous reaction products formed during post exposure bake to diffuse through the resist and the topcoat film without bubble formation or distortion of the
- topcoat (2) a low sodium metal or ammonium ion content ⁇ 100 ppm.
- Metallic or basic impurities in topcoat can desensitize the acid formed during exposure;
- Example 1 A lym film on silicon wafer of an acid catalyzed resist comprising poly-, p-tertbutyloxycarbonyloxystyrene resist containing 4% by weight of triphenysulfonium hexafluoroantimonate made in accordance with the method set forth in U.S. Patent 4,491,628 was exposed on Perkin-Elmer deep UV scanner (200-290 nm exposure band) and left standing for several minutes in a lab before post-exposure baking. After post expose baking and development in anisole, the 1 um lines of resist images were found to have overhanging "T" shapes.
- a companion wafer processed with a topcoat of 100 nm of polyvinylbutyral cast from butanol was found to form good straight wall profiles without "T" overhangs. hen the uncoated resist was exposed to longer periods of time of process air (25 hours) no images were formed in the uncoated resist film and only slight traces of overhang formation in the polyvinylbutyral topcoated acid catalyzed resist. A protection time of 30 minutes is considered adequate for even the slowest exposure tools.
- Example 2 - A l.O ⁇ m film on silicon wafer of an acid catalyzed resist comprising a partially t-butyloxycarbonyloxylated poly-p-hydroxystyrene sensitized with 8% MDT was exposed by Perkin-Elmer
- Example 3 A 1.0 y m film on a silicon wafer of the partially t-butyloxycarbonyloxylated poly-p-hydroxystyrene sensitized with MDT was exposed at 2.5 ⁇ C/c with a 25 KeV electrons. A faint image which was not developed out was formed. A similar
- Example 4 A l.O ⁇ m film on silicon of Ray PF
- topcoat polymeric materials which have the properties and performances as here set forth are within the teaching of the present invention and within its scope as set forth in the claims which follow.
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP91507106A JPH05507154A (en) | 1990-09-18 | 1990-12-21 | Protective film for acid catalyst resist |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US58727390A | 1990-09-18 | 1990-09-18 | |
US587,273 | 1990-09-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992005474A1 true WO1992005474A1 (en) | 1992-04-02 |
Family
ID=24349129
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1990/007618 WO1992005474A1 (en) | 1990-09-18 | 1990-12-21 | Top coat for acid catalyzed resists |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0556177A1 (en) |
JP (1) | JPH05507154A (en) |
CA (1) | CA2090039A1 (en) |
WO (1) | WO1992005474A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0703499A1 (en) * | 1994-09-23 | 1996-03-27 | Minnesota Mining And Manufacturing Company | Top coats for shoot and run printing plates |
GB2352825A (en) * | 1999-06-03 | 2001-02-07 | Hyundai Electronics Ind | Top coating composition for photoresist and process for forming fine pattern |
US6984482B2 (en) | 1999-06-03 | 2006-01-10 | Hynix Semiconductor Inc. | Top-coating composition for photoresist and process for forming fine pattern using the same |
DE102004030861A1 (en) * | 2004-06-25 | 2006-01-19 | Infineon Technologies Ag | Structuring a semiconductor substrate in a lithographic manner comprises preparing a semiconductor substrate, applying a first layer containing a photoresist and further processing |
US7514205B2 (en) | 2005-03-17 | 2009-04-07 | Jsr Corporation | Composition for forming antireflection film, laminate, and method for forming resist pattern |
US7709182B2 (en) | 2004-12-03 | 2010-05-04 | Jsr Corporation | Composition for forming antireflection film, layered product, and method of forming resist pattern |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2523719A1 (en) * | 1974-05-29 | 1975-12-11 | Fuji Photo Film Co Ltd | Pre-sensitised (lithographic) printing plates - with water-permeable org resin super-coat, improving keeping and handling props |
DE3216658A1 (en) * | 1981-05-07 | 1982-11-25 | Tokyo Shibaura Denki K.K., Kawasaki, Kanagawa | METHOD FOR PRODUCING A PHOTO PAINT PATTERN ON A SEMICONDUCTOR SUBSTRATE |
EP0290916A2 (en) * | 1987-05-12 | 1988-11-17 | Hoechst Aktiengesellschaft | Radiation-sensitive registration material |
-
1990
- 1990-12-21 EP EP19910906782 patent/EP0556177A1/en not_active Withdrawn
- 1990-12-21 JP JP91507106A patent/JPH05507154A/en active Pending
- 1990-12-21 WO PCT/US1990/007618 patent/WO1992005474A1/en not_active Application Discontinuation
- 1990-12-21 CA CA 2090039 patent/CA2090039A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2523719A1 (en) * | 1974-05-29 | 1975-12-11 | Fuji Photo Film Co Ltd | Pre-sensitised (lithographic) printing plates - with water-permeable org resin super-coat, improving keeping and handling props |
DE3216658A1 (en) * | 1981-05-07 | 1982-11-25 | Tokyo Shibaura Denki K.K., Kawasaki, Kanagawa | METHOD FOR PRODUCING A PHOTO PAINT PATTERN ON A SEMICONDUCTOR SUBSTRATE |
EP0290916A2 (en) * | 1987-05-12 | 1988-11-17 | Hoechst Aktiengesellschaft | Radiation-sensitive registration material |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0703499A1 (en) * | 1994-09-23 | 1996-03-27 | Minnesota Mining And Manufacturing Company | Top coats for shoot and run printing plates |
US5939237A (en) * | 1994-09-23 | 1999-08-17 | Imation Corp. | Top coats for shoot and run printing plates |
GB2352825A (en) * | 1999-06-03 | 2001-02-07 | Hyundai Electronics Ind | Top coating composition for photoresist and process for forming fine pattern |
GB2352825B (en) * | 1999-06-03 | 2003-12-17 | Hyundai Electronics Ind | Top-coating composition for photoresist and process for forming fine pattern using the same |
US6984482B2 (en) | 1999-06-03 | 2006-01-10 | Hynix Semiconductor Inc. | Top-coating composition for photoresist and process for forming fine pattern using the same |
US7329477B2 (en) | 1999-06-03 | 2008-02-12 | Hynix Semiconductor Inc. | Process for forming a fine pattern using a top-coating composition for a photoresist and product formed by same |
DE102004030861A1 (en) * | 2004-06-25 | 2006-01-19 | Infineon Technologies Ag | Structuring a semiconductor substrate in a lithographic manner comprises preparing a semiconductor substrate, applying a first layer containing a photoresist and further processing |
US7709182B2 (en) | 2004-12-03 | 2010-05-04 | Jsr Corporation | Composition for forming antireflection film, layered product, and method of forming resist pattern |
US7514205B2 (en) | 2005-03-17 | 2009-04-07 | Jsr Corporation | Composition for forming antireflection film, laminate, and method for forming resist pattern |
Also Published As
Publication number | Publication date |
---|---|
EP0556177A1 (en) | 1993-08-25 |
JPH05507154A (en) | 1993-10-14 |
CA2090039A1 (en) | 1992-03-19 |
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