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
• • 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
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition

Definitions

• the present invention pertains to a photoresist composition, in particular, for the production of semiconductor devices.
• the present invention also pertains to photoacid generators which are useful in photoresists particularly for imaging with exposure to light at relatively short wavelengths, e.g. ,157 nm.
• Polymer products are used as components of imaging and photosensitive systems and particularly in photoimaging systems such as those described in Introduction to Microlithoqraphv, Second Edition by L. F. Thompson, C. G. Willson, and M. J. Bowden, American Chemical
• UV light or other electromagnetic radiation impinges on a material containing a photoactive component to induce a physical or chemical change in that material.
• a useful or latent image is thereby produced which can be processed into a useful image for semiconductor device fabrication.
• a photosensitive composition contains one or more photoactive components in addition to the polymer product.
• the photoactive component Upon exposure to electromagnetic radiation (e.g., UV light), the photoactive component acts to change the rheologicai state, solubility, surface characteristics, refractive index, color, electromagnetic characteristics or other such physical or chemical characteristics of the photosensitive composition as described in the Thompson et al. publication.
• UV far or extreme ultraviolet
• Positive working photoresists generally are utilized for semiconductor manufacture.
• Lithography in the UV at 365 nm (l-line) using novolak polymers and diazonaphthoquinones as dissolution inhibitors is a currently established chip technology having a resolution limit of about 0.35-0.30 micron.
• Lithography in the far UV at 248 nm using p-hydroxystyrene polymers is known and has a resolution limit of 0.35-0.18 nm.
• Photolithography using 193 nm exposure wavelength is a leading candidate for future microelectronics fabrication using 0.18 and 0.13 ⁇ m design rules.
• Photolithography using 157 nm exposure wavelength is a leading candidate for future microlithography (beyond 193 nm) provided suitable materials can be found having sufficient transparency and other required properties at this very short wavelength.
• a photoactive component is usually utilized in the photoresist composition. It typically is a compound that produces either acid or base upon exposure to actinic radiation. If an acid is produced upon exposure to actinic radiation, the PAC is termed a photoacid generator (PAG). If a base is produced upon exposure to actinic radiation, the PAC is termed a photobase generator (PBG).
• PAG photoacid generator
• PBG photobase generator
• photoacid generators include, but are not limited to, compounds represented by the structures below:
• R-1-R3 are independently substituted or unsubstituted aryl or substituted or unsubstituted C-
• Representative aryl groups include, but are not limited to, phenyl and naphthyl.
• Suitable substituents include, but are not limited to, hydroxyl (-OH) and C-j-C 2 rj alkyloxy (e.g., C-
• the anion X- in structures l-ll can be, but is not limited to, SbFg " (hexafluoroantimonate), CF3SO3-
• the invention provides a photoresist composition
• the invention is directed to a photoresist composition
• a photoresist composition comprising: (a) a polymeric binder; and (b) a photoactive component selected from the group consisting of: (a) a hydroxamic acid sulfonoxy ester represented by the structure:
• X OSO 2 R f
• Y R, NO 2 , CN, halogen atom, -C(O)OR, -SO 2 O", or R f ;
• the invention in another aspect, relates to a process for forming a relief image on a substrate having a photoresist layer comprising, in order: (a) imagewise exposing the photoresist layer to form imaged and non- imaged areas, wherein the photoresist layer is prepared from a photoresist composition comprising (b) a polymeric binder; and (c) a photoactive component selected from the group consisting of (a) the hydroxamic acid sulfonoxy ester containing the R f group; (b) the S-perfluoroalkyldibenzothiophenium salt and (c) the
• the polymeric binder has an absorption coefficient of less than about 4.0 ⁇ nr 1 at a wavelength of 157 nm, typically, less than about 3.5 ⁇ nrr 1 at a wavelength of 157 nm and even more typically, less than about 3.0 ⁇ nrr 1 at a wavelength of 157 nm.
• the photoresist compositions of the invention comprise a polymeric binder and a photoactive component.
• binders useful for this invention comprise any polymer which has the transparency properties suitable for use in microlithography. It is contemplated that binders suitable for the present invention may include those polymers which are typically incorporated into chemically amplified 248 (deep UV) and 193 nm photoresists for imaging at longer wavelengths.
• a typical 248 nm photoresist binder is based on polymers of para-hydroxystyrene.
• Other examples of suitable 248 nm photoresist binders can be found in the reference Introduction to Microlithography, Second Edition by L. F. Thompson, C. G. Willson, and M. J. Bowden, American Chemical Society, Washington, DC, 1994, chapter 3.
• Binders useful for 193 nm photoresists include cycloolefin-maleic anhydride alternating copolymers [such as those disclosed in F. M. Houlihan et al., Macromolecules, 30, pages 6517-6534 (1997); T. Wallow et al., Proc. SPIE, 2724, 355; and F. M. Houlihan et al., Journal of Photopolymer Science and Technology, 10, 511(1997)], polymers of functionalized norbomene-type monomers prepared by metal-catalyzed vinyl addition polymerization or ring-opening metathesis polymerization [such as those disclosed in U. Okoroanyanwu et al.J Mol. Cat.
• Photoresist binders that are suitable for use with this invention also include those which are transparent at wavelengths below 248 and 193 nm such as those polymers containing fluoroalcohol functional groups [such as those disclosed in K. J. Pryzbilla et al. Proc. SPIE 1672, 9 (1992), and H. Ito et al. Polymn. Mater. Sci. Eng. 77, 449 (1997)].
• Typical examples of polymers which are also useful are those which have been developed for use in chemically amplified photoresists which are imaged at an irradiation wavelength of 157 nm.
• Examples of such polymers are fluoropolymers and fluoropolymers containing fluoroalcohol functional groups. Suitable examples have been disclosed in WO 00/17712 and WO 00/25178.
• the quantity of polymeric binder in the photoresist composition may be in the amount of about 50 to about 99.5 weight % based on the weight of the total photoresist composition (solids).
• Photoactive Component (PAC) Photoactive Component
• the photoresist composition contains a combination of binder and photoactive component.
• the photoactive component may be (1) a hydroxamic acid sulfonoxy ester represented by the structure:
• Rf C m F 2m+1 and m is an integer of 5 to about 10, more typically m ranges from 5 to 8.
• R group include perfluoropentyl, perfluorohexyl, perfluoroheptyl, and perfluorooctyl.
• hydroxamic acid sulfonoxy esters represented by the above structure include N-perfluoropentylsulfonyloxy-phthaleimid, N- perfluorohexyl-sulfonyloxyphthaleimid, N-perfluoroheptyl- sulfonyloxyphthaleimid, and N-perfluorooctylsulfonyloxyphthaleimid.
• These compounds may be prepared by reaction of the thallous salt of N- hydroxyphtalimide and the anhydride of triflic acid in methylene chloride as a solvent by known methods, for example as reported in J. Org. Chem., 38 ⁇ 1973> 22, 3908-3911 by Chapman, T.M.; Freedman, E.A.
• the photoactive component may be an S-perfluoroalkyldibenzothiophenium salt represented by the structure:
• Y halogen atom, such as F, Cl, Br, I; R group; NO 2 ; CN; - C(O)OR, SO 2 O" or R f ; wherein R is C p H 2p+ - ⁇ , wherein p is an integer ranging from 1 to about 10, typically from 1 to about 5 such as CH 3 , C 2 H 5 , C3H7, etc.
• R f C n F 2n+ -
• n an integer of 1 to about 10
• S-(trifluoromethyl)dibenzothiophenium triflate trifluoromethane sulfonate
• halogen atom such as fluorine, chlorine, bromine, iodine
• alkyl designated by the group R which is CpH 2p+ ⁇ , wherein p is an integer ranging from 1 to about 10, typically from 1 to about 5 such as
• S-(perfluoroalkyl)dibenzothiophenium salts can be achieved for example by introduction of nitro- or sulfonato- groups into the 3 and 7 position of an aromatic system by reaction of S-(perfluoroaIkyl)dibenzothiophenium salts with fumic sulfuric acid at 40°C, followed by nitration of product by a mixture of fumic sulfuric and concentrated nitric acids at ambient temperature. This procedure was reported in Journal of Fluorine Chemistry, 1995, v.74, p.77 by T.Umemoto, S. Ishihara and K. Adachi.
• the photoactive component may be S-perfluoroalkyldiarylsulfonium salts represented by the structure:
• Some suitable compounds represented by the above structure include, but are not limited to, S-trifluoromethyldiphenylsuIfonium triflate S-(pentalfuoroethyl)diphenylsulfonium pentafluoroethylsulfonate, S-(heptafuoroprpopyl)diphenylsulfonium nonafluorobutylsulfonate, S-(nonafluorobutyl)diphenylsulfonium perfluorooctylsulfonate etc.
• phenyl rings may carry different substituents in the phenyl rings such as halogen atom (such as fluorine, chlorine, bromine, iodine), alkyl designated by the group R which is C p H 2p+1 , wherein p is an integer ranging from 1 to about 10, typically from 1 to about 5 such as CH 3 , C 2 H 5 , C 3 H 7 , etc., -CN, -C(O)OR, nitro, perfluoroalky
• halogen atom such as fluorine, chlorine, bromine, iodine
• alkyl designated by the group R which is C p H 2p+1 , wherein p is an integer ranging from 1 to about 10, typically from 1 to about 5 such as CH 3 , C 2 H 5 , C 3 H 7 , etc.
• -CN, -C(O)OR nitro, perfluoroalky
• (S-trifluoromethyl)diphenylsulfonium triflate may be by reaction of phenyltrifluoromethylsulfoxide and benzene in triflic anhydride at ambient temperature. This procedure was reported in Journal American Chemical Society 1993, v.115 p. 2156-2164 by T.Umemoto and S. Ishihara.
• the photoactive compound may be present in the amount of about 0.5 to about 10% by weight typically about 1 to about 5% by weight, based on the total dry weight of photoresist composition.
• dissolution inhibitors can be utilized in this invention.
• dissolution inhibitors (Dls) for the far and extreme UV photoresists are selected to satisfy multiple needs including dissolution inhibition, plasma etch resistance, and adhesion behavior of photoresist compositions comprising a given Dl additive.
• a dissolution inhibitor is included in a photoresist composition to assist in the development process.
• a good dissolution inhibitor will inhibit the unexposed areas of the photoresist layer from dissolving during the development step in a positive working system.
• a useful dissolution inhibitor may also function as a plasticizer which function provides a less brittle photoresist layer that will resist cracking.
• Some dissolution inhibiting compounds also serve as plasticizers in photoresist compositions.
• Bile-salt esters are particularly useful as dissolution inhibitors in the compositions of this invention.
• Bile- salt esters are known to be effective dissolution inhibitors for deep UV photoresists, beginning with work by Reichmanis et al. in 1983. (E. Reichmanis et al., "The Effect of Substituents on the Photosensitivity of 2-Nitrobenzyl Ester Deep UV Resists", J. Electrochem. Soc.
• Bile-salt esters are particularly attractive choices as dissolution inhibitors for several reasons, including their availability from natural sources, their possessing a high alicyclic carbon content, and particularly for their being transparent in the deep and vacuum UV region, (which essentially is also the far and extreme UV region), of the electromagnetic spectrum (e.g., typically they are highly transparent at 193 nm). Furthermore, the bile-salt esters are also attractive dissolution inhibitor choices since they may be designed to have widely ranging hydrophobic to hydrophilic compatibilities depending upon hydroxyl substitution and functionalization.
• Representative bile-acids and bile-acid derivatives that are suitable as dissolution inhibitors for this invention include, but are not limited to, those illustrated below, which are as follows: cholic acid (IV), deoxycholic acid (V), lithocholic acid (VI), t-butyl deoxycholate (VII), t-butyl lithocholate (VIII), and t-butyl-3- ⁇ -acetyl lithocholate (IX).
• Bile-acid esters, including compounds VII-IX, are preferred dissolution inhibitors in this invention.
• compositions of this invention can contain optional additional components.
• additional components include, but are not limited to, resolution enhancers, adhesion promoters, residue reducers, coating aids, plasticizers, and T g (glass transition temperature) modifiers.
• Crosslinking agents may also be present in negative-working photoresist compositions.
• crosslinking agents include bis-azides, such as,4,4'-diazidodiphenyl sulfide and 3,3'- diazidodiphenyl sulfone.
• the photoresist composition can include an amount of solvent, typically an organic solvent such as cyclohexanone.
• the solvent is usually used in an amount sufficient to dissolve the binder and the photoactive component.
• a specific solvent found to be useful is cyclohexanone.
• photoresist layer imagewise exposing a photoresist layer to form imaged and non-imaged areas, wherein the photoresist layer is prepared from a photoresist composition comprising: (a) a polymeric binder; and
• the photoresist layer is prepared by applying a photoresist composition onto a substrate and drying to remove the solvent.
• the photoresist layer is, typically, applied by spin coating onto a substrate, typically a silicon wafer having a primer applied thereon.
• the so formed photoresist layer is sensitive in the ultraviolet region of the electromagnetic spectrum and especially to those wavelengths ⁇ 365 nm. Imagewise exposure of the photoresist compositions of this invention can be done at many different UV wavelengths including, but not limited to, 365 nm,
• Imagewise exposure is preferably done with ultraviolet light of 248 nm, 193 nm, 157 nm, or lower wavelengths, preferably it is done with ultraviolet light of 193 nm, 157 nm, or lower wavelengths, and most preferably, it is done with ultraviolet light of 157 nm or lower wavelengths.
• Imagewise exposure can either be done digitally with a laser or equivalent device or non-digitally with use of a photomask. Digital imaging with a laser is preferred.
• Suitable laser devices for digital imaging of the compositions of this invention include, but are not limited to, an argon-fluorine excimer laser with UV output at 193 nm, a krypton-fluorine excimer laser with UV output at 248 nm, and a fluorine (F 2 ) laser with output at 157 nm. Since, as discussed supra, use of UV light of lower wavelength for imagewise exposure corresponds to higher resolution (lower resolution limit), the use of a lower wavelength (e.g., 193 nm or 157 m or lower) is generally preferred over use of a higher wavelength (e.g., 248 nm or higher).
• the photoresist compositions of this invention must contain sufficient functionality for development following imagewise exposure to UV light.
• the functionality is an acid or protected acid such that aqueous development is possible using a basic developer such as sodium hydroxide solution, potassium hydroxide solution, or ammonium hydroxide solution, such as tetramethylammonium hydroxide.
• the binder material should contain sufficient acid groups (e.g., fluoroalcohol groups) and/or protected acid groups that are at least partially deprotected upon exposure to render the photoresist (or other photoimageable coating composition) processable in aqueous alkaline developer.
• the photoresist layer will be removed during development in portions which are exposed to UV radiation but will be substantially unaffected in unexposed portions during development by aqueous alkaline liquids such as wholly aqueous solutions containing 0.262 N tetramethylammonium hydroxide (with development at 25°C usually for less than or equal to 120 seconds).
• aqueous alkaline liquids such as wholly aqueous solutions containing 0.262 N tetramethylammonium hydroxide (with development at 25°C usually for less than or equal to 120 seconds).
• the photoresist layer will be removed during development in portions which are unexposed to UV radiation but will be substantially unaffected in exposed portions during development using either a critical fluid or an organic solvent.
• a critical fluid is one or more substances heated to a temperature near or above its critical temperature and compressed to a pressure near or above its critical pressure.
• Critical fluids in this invention are at least at a temperature that is higher than 15°C below the critical temperature of the fluid and are at least at a pressure higher than 5 atmospheres below the critical pressure of the fluid.
• Carbon dioxide may be used for the critical fluid in the present invention.
• Various organic solvents can also be used as developer in this invention. These include, but are not limited to, halogenated solvents and non-halogenated solvents. Halogenated solvents are typical and fluorinated solvents are more typical.
• the substrate employed in this invention can be any material used in semiconductor manufacture, for example, a wafer usually made from silicon, silicon oxide, silicon nitride and the like. Usually, a primer is applied to the silicon wafer.
• a typical primer composition is hexamethyldisilazane.
• a copolymer of a norbornene fluoroalcohol monomer (NB-F-OH) and a methoxy methyl ether-protected norbornene fluoroalcohol monomer (NB-F-OMOM) was used.
• the copolymer was made according to a procedure similar to that described in Example 27 WO 00/67072.
• the NB-F-OH monomer was made in accordance with Example 13 of WO 00/67072 and the methoxymethylether monomer (NB-F-OMOM) was made in accordance with Example 14 of WO 00/67072.
• the resulting copolymer was formulated into a photoresist composition by preparing a solution of the following components which were combined and magnetically stirred overnight.
• the wafer was prepared by depositing about 0.75 ml of hexamethyldisilazane (HMDS) primer and spinning at 3000 rpm for 60 seconds. Then about 0.5 ml of the above solution, after filtering through a 0.45 ⁇ m glass syringe filter, was deposited and spun at 3000 rpm for 60 seconds and baked at 120°C for 60 seconds.
• HMDS hexamethyldisilazane
• 248 nm imaging was accomplished by exposing the coated wafer to light obtained by passing broadband UV light from an ORIEL Model-82421 Solar Simulator (1000 watt) through a 248 nm interference filter which passes about 30% of the energy at 248 nm. Exposure time was 30 seconds, providing an unattenuated dose of 20.5 mJ/cm 2 . By using a mask with 18 positions of varying neutral optical density, a wide variety of exposure doses were generated. After exposure the exposed wafer was baked at 100°C for 60 seconds.
• TMAH tetramethylammonium hydroxide

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