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
  • G03F7/075—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
  • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains

Definitions

• the invention relates to a polymerizable composition according to the preamble of claim 1, a polymer according to claim 6, a resist according to claim 7 and a lithography method according to the preamble of claim 11.
• Photomasks such as those used in semiconductor lithography, currently mostly consist of a transparent quartz glass plate to which a structured, non-transparent chrome layer is applied (COG: Chrome on Glass). So-called mask blanks are used in the manufacturing process; These are quartz glass plates, which are covered with a continuous / chrome layer that is currently approx. 30 to 100 nm thick.
• COG Chrome on Glass
• These mask blanks are coated with a light or electron sensitive photoresist (resist) and e.g. using a laser or electron beam recorder to describe it in a targeted manner with any layout.
• the photoresist layer is then developed and, in the case of the positive resist, the photoresist is removed at the points described above. In the case of a negative resist, however, the varnish is removed from the unexposed areas.
• the result is a relief-like image of the previously written structure in the photoresist;
• the photoresist now protects the chrome layer at defined points (depending on the resist system, the previously exposed or unexposed), whereas the chrome is exposed between these points and can be further processed in a targeted manner.
• the further treatment in mask production is a targeted removal of the chrome layer by plasma etching.
• the structure previously created in the resist is transferred into the chromium layer by removing the exposed (not protected by resist) chromium in a reactive ion plasma consisting, for example, of a chlorine / oxygen gas mixture.
• Chromium-halogen oxides are transferred in order to be effectively removed in the end.
• this high oxygen content attacks the photoresist on the chrome very strongly, so that it is also gradually removed, particularly laterally.
• Resist lines are e.g. "Shrinked" by values of approximately 30 to 60 nm per edge. This reduced geometry is also transferred to the chrome layer, so that after the etching process, the authenticity of the chrome structures (compared to the theoretical
• Layout structure is not guaranteed. As a frequently occurring rule of thumb, approximately 50 nm loss (overetching) currently occurs per structure edge; which means that structure lines are generally approx. 100 nm narrower after etching than the theoretical layout.
• OPC Optical Proximity Correction Features
• the present invention has for its object to provide a resist and an electron writing method with which the etching loss can be reduced.
• a resist with the features of claim 1.
• the subject matter of claim 1 is a monomer of a resist which solves the problem of chromium etching loss through a significantly increased etching stability compared to the chlorine / oxygen plasmas used in mask production.
• the invention solves the problem by using a special monomer with which resist with a greatly increased stability compared to the etching plasmas used is used.
• the proposed photoresist contains chemically bound silicon. Surprisingly, this results in a significantly increased etching stability in the final chrome etching process compared to all other commercial lacquers.
• the silicon is oxidized in the highly oxygen-containing etching plasma to form non-volatile silicon dioxide, which greatly limits or prevents the lateral resist shrinkage.
• the resist and chromium etching loss is limited to almost zero, which means that no structural reserve has to be written in the electron beam writing process.
• the requirements for the mask writing resolution are reduced to such an extent that the future technology generations of the 70 and 50 nm masks can be mastered with the mask writing devices. Without the reduction of the chrome etching loss, the future devices would not be able to cope with these technology deaths due to the still existing resolution limitation.
• Ri, R 2 , R 3 H or alkyl radicals (preferably H or methyl radicals)
• R 4 , R 5 alkyl radicals (preferably methyl radicals), or further silicon units, for example siloxane units
• R 6 alkyl radical (preferably tert-butyl radical)
• R 7 H or alkyl radical (preferably methyl radical)
• These monomers can be, for example, by radical polymerization with themselves or together with others
• Monomers e.g. maleic anhydride, styrene, p-hydroxystyrene, methacrylic acid or the like
• Monomers are simply polymerized and thus used as the basic component in resists according to the invention.
• the silicon content in the polymer By increasing the silicon content in the polymer, the dimensional stability of the lacquer layer is improved. It can be expected that the silicon content is between 5-25% by weight depending on the monomer used.
• a typical resist mix can e.g. consist of:
• solvent methoxypropyl acetate, ethyl acetate, ethyl lactate, cyclohexanone, gamma-butyrolactone, methyl ethyl ketone, etc.
• the resist can be used in a laser or electron beam lithography process.
• photo acid generator e.g. Crivello salts, triphenyl sulfonium sulfonates, diphenyl iodonium sulfonates, phthalimidosulfonates, ortho-nitrobenzyl sulfonates, or the like
• the resist can be used in a laser or electron beam lithography process.
• a mask blank is coated with the resist solution according to the invention. Then the resist is written with a laser and / or
• Electron beam recorder A heating step can, but does not have to be carried out subsequently.
• the resist described is then washed with an aqueous alkaline developer medium (e.g. 2.38% aqueous tetraethylammonium hydroxide solution,
• Standard TMAH developer e.g. using a reactive ion plasma (RIE) to dry-etch the mask blank with a chlorine / oxygen gas mixture.
• RIE reactive ion plasma
• the ethereal phase is separated off via a separating funnel and dried over calcium chloride for 24 hours. It is filtered off and the filtrate is added dropwise to an ice-cooled solution of 50 mmol of di-butyl pyrocarbonate in anhydrous diethyl ether within 1 h. The reaction mixture is shaken thoroughly 3 times with water, then the organic phase is separated off in a separating funnel and again dried over calcium chloride for 24 hours. Rotating off the diethyl ester gave the product with strong impurities as a yellowish liquid.
• This polymer can be used as a base component for mixing resist.
• the embodiment of the invention is not limited to the preferred exemplary embodiments specified above. Rather, a number of variants are conceivable which make use of the polymerizable composition according to the invention, the polymer, the resist and the lithographic process even in the case of fundamentally different types.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
• Materials For Photolithography (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (3)

Publications (1)

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• 2002
  • 2002-07-22 DE DE10233849A patent/DE10233849B4/de not_active Expired - Fee Related
• 2003
  • 2003-06-24 TW TW092117184A patent/TW200403525A/zh unknown
  • 2003-07-21 KR KR1020057001013A patent/KR100860759B1/ko not_active IP Right Cessation
  • 2003-07-21 WO PCT/DE2003/002502 patent/WO2004017142A1/de active Application Filing
  • 2003-07-21 JP JP2004528437A patent/JP2006509845A/ja active Pending
  • 2003-07-21 US US10/520,534 patent/US7374858B2/en not_active Expired - Fee Related
  • 2003-07-21 AU AU2003250802A patent/AU2003250802A1/en not_active Abandoned
  • 2003-07-21 EP EP03787737A patent/EP1523698A1/de not_active Withdrawn
  • 2003-07-21 CN CNA03817362XA patent/CN1675589A/zh active Pending

Non-Patent Citations (1)

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