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
  • G03F7/038—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
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
• • 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
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
• • 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
  • G03F7/0046—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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
• • 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
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• microelectronic devices are fabricated in smaller geometries there is an increasing demand for advanced materials that meet the stringent requirements of confined smaller geometries.
• sub-micron device geometries have become common place in the fabrication of a variety of microelectronics packages for memory and logic integrated circuits (ICs), liquid crystal displays (LCDs), organic light emitting diodes (OLEDs) and other radio frequency (Rf) and microwave devices.
• ICs memory and logic integrated circuits
• LCDs liquid crystal displays
• OLEDs organic light emitting diodes
• Rf radio frequency
• devices such as radio frequency integrated circuits (RFICs), micro-machine integrated circuits (MMICs), switches, couplers, phase shifters, surface acoustic wave (SAW) filters and SAW duplexers, have recently been fabricated with submicron dimensions.
• RFICs radio frequency integrated circuits
• MMICs micro-machine integrated circuits
• switches couplers, phase shifters, surface acoustic
• A is a monomeric repeat unit and Y is a pendent acidic group selected from phenolic hydroxyl group, carboxylic acid group and a sulfonic acid group;
• a is an integer from 1 to 3;
• M and Mi are the same or different and independently of each other selected from the group consisting of substituted or unsubstituted (C2-Cs)alkenyl, (C3-Cs)cycloalkenyl, (C 7 -Ci2)bicycloaIkenyl and (C 7 -Ci2)tricycloalkenyl where said substituents are selected from (Ci-C 6 )alkyl, (Ci-C 6 )alkoxy, (C 2 -C 6 )alkenyl, (C 3 -C 8 )cycloalkenyl, (C 7 -Ci 2 )bicycloalkenyl, (C i -Ce)alkoxy(C3-C6)alkeny 1, (C i -C6)alkoxy(C 3 -C 8 )cycloalkeny 1 and
• B and Bi are the same or different and independently of each other is a bond or a divalent group selected from the group consisting of (CZ 2 )b, (CZ 2 0) b , (CZ 2 S)b, (OCZ 2 )b,
• D is selected from the group consisting of ethyl, a fluorinated or perfluorinated methyl or ethyl, a linear or branched (C 3 -C 2 s)hydrocarbyl, a linear or branched fluorinated or perfluorinated (C 3 -C 25 )hydrocarbyl group, and substituted or unsubstituted (C6-Ci 8 )cyclic or polycyclic hydrocarbyl group; and
• FIG. 1 shows an optical micrograph of a negative tone lithographic images of line and space pattern obtained from a composition embodiment of this invention.
• FIG. 2 shows an optical micrograph of a negative tone lithographic images of line and space pattern obtained from another composition embodiment of this invention.
• FIG. 3 shows an optical micrograph of a negative tone lithographic images of line and space pattern obtained from yet another composition embodiment of this invention.
• FIG. 4 shows an optical micrograph of a negative tone lithographic images of line and space pattern obtained from yet another composition embodiment of this invention.
• FIG. 5 shows an optical micrograph of a negative tone lithographic images of line and space pattern obtained from yet another composition embodiment of this invention.
• FIG. 6 shows an optical micrograph of a negative tone lithographic images of line and space pattern obtained from yet another composition embodiment of this invention.
• Embodiments in accordance with the present invention are directed to various compositions, including but not limited to, polymers that encompass at least one repeating unit of formula (I) containing an acidic pendent group as described herein, at least one reactive olefmic compound of formulae (II), (III) or (IV) as described herein and at least one photoacid generator.
• Such compositions being capable of forming self-imageable films useful as layers in the manufacture of microelectronic and optoelectronic devices. That is to say that, after image- wise exposure to actinic radiation, such layers (or films) can be developed to form patterned layers (or films), where such pattern is reflective of the image through which the layers (or films) was exposed. In this manner, structures can be provided that are, or are to become, a part of such microelectronic and/or optoelectronic devices.
• Exemplary sub-ranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, etc.
• the symbol " . vw” denotes a position at which the bonding takes place with another repeat unit or another atom or molecule or group or moiety as appropriate with the structure of the group as shown.
• (Ci-Ci5)alkyl includes methyl and ethyl groups, and straight-chained or branched propyl, butyl, pentyl, hexyl, heptyl, and various other homolog groups.
• Particular alkyl groups are methyl, ethyl, n-propyl, isopropyl and tert-butyl, etc.
• (C 2 -C6)alkenyl includes ethenyl and straight-chained or branched propenyl, butenyl, pentenyl and hexenyl groups.
• (C 2 - C6)alkynyl includes ethynyl and propynyl, and straight-chained or branched butynyl, pentynyl and hexynyl groups.
• (Ci-Ci5)perfluoroalkyl means that all of the hydrogen atoms in said alkyl group are replaced with fluorine atoms. Illustrative examples include trifluoromethyl and pentafluoroethyl, and straight-chained or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl groups. Derived expression, "(Ci- Cis)perfluoroalkoxy”, is to be construed accordingly.
• the expression "(C6-Cio)aryl means substituted or unsubstituted phenyl or naphthyl.
• photodefinable refers to the characteristic of a material or composition of materials, such as a polymer composition in accordance with embodiments of the present invention, to be formed into, in and of itself, a patterned layer or a structure.
• a photodefinable layer does not require the use of another material layer formed thereover, for example a photoresist layer, to form the aforementioned patterned layer or structure.
• a polymer composition having such a characteristic be employed in a pattern forming scheme to form a patterned film/layer or structure. It will be noted that such a scheme incorporates an "imagewise exposure" of the photodefinable material or layer. Such imagewise exposure being taken to mean an exposure to actinic radiation of selected portions of the layer, where non- selected portions are protected from such exposure to actinic radiation.
• A is a monomeric repeat unit and Y is a pendent acidic group selected from phenolic hydroxyl group, carboxylic acid group and a sulfonic acid group;
• a is an integer from 1 to 3;
• M and Mi are the same or different and independently of each other selected from the group consisting of substituted or unsubstituted (C2-Cg)alkenyl, (C3-Ce)cycloalkenyl,
• R 2 and R 3 are independently of each other H , methyl, ethyl or a linear or branched (C 3 -Ci 2 )alkyl group and such that O, NRi and/or S atoms are not linked directly to one another;
• any of the polymers which carry a pendent acidic group of the formula (I) can be used in combination with one or more of the compounds of formulae (II), (III) or (IV) in order to form the compositions in accordance with this invention. It is envisioned that the acidic group reacts with one or more of the olefinic functional group contained in the compounds of formula (II), (III) or (IV) in order to form an addition compound when exposed to suitable actinic radiation in the presence of a photoacid generator as shown in Scheme I, where such addition reaction is illustrated with a representative compound of formula (II), where M and Mi are both C 3 -alkenyl group, resulting in an addition product A. Accordingly, any of the polymers which contain a pendent acidic groups that brings about such an addition reaction can be employed in this invention.
• the starting polymer is aqueous base soluble and the resulting addition product after actinic radiation is base insoluble, i.e., the exposed negative tone images are insoluble in base.
• the compositions of this inventions can be readily developed using any of the commonly used aqueous base developers as further described hereinbelow.
• the compositions of this invention can also be used with any of the organic solvents as both carrier solvents and as developing solvents as is commonly used in the art.
• any polymer with an acidic pendent group having a pKa of about ten or less is suitable to form the compositions of this invention.
• the pKa of the acidic pendent group is in the range from about 1 to 10, in some other embodiments the pKa of the acidic pendent group is from about 3 to 8.
• acidic pendent group include without any limitation substituted or unsubstituted phenolic pendent group, carboxylic acid pendent group, sulfonic acid pendent group, sulfonamide pendent group, and the like.
• Substituted phenolic pendent group which is substituted with electronic withdrawing groups such as halogen, CN, halogenated or perhalogenated alkyl groups is more acidic than the unsubstituted phenolic pendent group.
• electron donating substituent such as alkyl or alkoxy group results in lesser acidity of the pendent phenolic group. Accordingly, any of the polymers containing suitably substituted phenolic pendent group with a pKa of less than ten are suitable for forming the compositions of this invention.
• polymers of formula (I) include without any limitation all known homo- and copolymers of polyacrylic acid, polymethacrylic acid, poly(hydroxystyrene), polynorbornenes containing pendent phenolic, carboxylic acid, hydroxy, sulfonic acid and sulfamic acid and sulfonamide groups, and polymers having the repeat units of ring opened maleic anhydride groups, among other polymers.
• any of the olefmic compounds of formulae (II), (III) or (IV) which reacts with a polymer of formula (I) can be used in forming the compositions of this invention.
• the compositions of this invention are suitable in a variety of electronic applications where temperatures in excess of 150°C or higher or employed. Accordingly, a compound of formulae
• composition of this invention is first applied on to a suitable substrate and then post apply baked to remove the solvent, generally in the temperature range of from about 80 to 150 °C. Accordingly, it is very desirable that the compound of formulae (II),
• the compounds of formulae (II), (III) or (IV) featuring low vapor pressure than some of the solvents employed are more suitable in the compositions of this invention.
• the solvents employed herein as further discussed in detail below may have vapor pressures as low as 0.5 mm Hg at room temperature.
• PGMEA propylene glycol methyl ether acetate
• GBL ⁇ -butyrolactone
• a compound of formulae (II), (III) or (IV) which has a vapor pressure less than the vapor pressure of the solvent employed herein such that any step that requires removal of solvent post-coating of the composition onto a substrate and pre-exposure to actinic radiation does not also remove the compound of formulae (II), (III) or (IV).
• the vapor pressure of the compound of formulae (II), (III) or (IV) is less than 5 mm Hg at ambient room temperatures, such as for example, in the temperature range of 20 to 25°C.
• the vapor pressure of the compound of formulae (II), (III) or u (IV) is less than 1 mm Hg at ambient room temperatures, such as for example in the temperature range of 20 to 25°C.
• olefinic monomers such as for example norbornene which has a vapor pressure of 39 mm Hg at 25 °C and norbomadiene which has a vapor pressure of 25 mm Hg at 25 °C are not suitable to be used as reactive olefinic monomers in place of one or more compounds of formulae (II), (III) or (IV).
• the polymer compositions of this invention further contains a photoacid generator (PAG).
• PAG photoacid generator
• the PAG that can be employed in this invention is ionic or non-ionic compound which when exposed to suitable radiation releases free acid.
• Non-limiting examples of polymers of formula (I) that can be employed in the composition of this invention are selected from the group consisting of:
• ⁇ vw represents a position at which the bonding takes place with another repeat unit
• RA is selected from -(CH 2 ) v -C0 2 R4a, -(CH 2 ) v -Ar-OH, -(CH 2 ) v -C(0)-Ar-OH,
• R5, R6, R7 and R 8 are the same or different and independently of each other selected from the group consisting of hydrogen, methyl, ethyl, a fluorinated or perfluorinated methyl or ethyl, a linear or branched substituted or unsubstituted
• R9 is selected from the group consisting of hydrogen, methyl, ethyl, a fluorinated or perfluorinated methyl or ethyl, a linear or branched (C3-C9)hydrocarbyl, a linear or branched fluorinated or perfluorinated (C3-C9)hydrocarbyl group, and substituted or unsubstituted (Ce- Cie)cyclic or polycyclic hydrocarbyl group;
• Rio and Rn are the same or different and are selected from hydrogen, methyl, ethyl, a fluorinated or perfluorinated methyl or ethyl and a linear or branched (C3-C9)hydrocarbyl.
• the first class of polymers containing a repeat unit of formula (la) various poly(para-hydroxystyrene) polymers are known in the literature, and all of such polymers can be employed in the compositions of this invention. See, for example, U. S. Patent No. 4,898,916, which discloses a process for the preparation of homopolymers of poly(para- hydroxystyrene) from poly(para-acetoxystyrene).
• Various copolymers containing the repeat unit of formula (la) are disclosed in U.S. Patent No. 4,877,843 and U. S. Patent No. 4,857,601, pertinent portions of which are incorporated herein by reference.
• composition of this invention encompasses a compound of formula (II), which is selected from the group consisting of:
• K is selected from CH 2 , CH 2 -CH 2 , O and S;
• X is O, S, NRi, SiR 2 R 3 , -(CZ 2 ) b - where Z and b are as defined above , -C(O)-,
• b is an integer from 0 to 5;
• b is an integer from 0 to 5
• d is independently a single bond or double bond
• X is as defined above.
• Non-limiting examples of the compound of formula (II) maybe selected from the group consisting of:
• n 2 to 4:
• R and R' are independently selected from (G-Ci2alkyl), (Ce-Cioaryl) and
• compositions of this invention further encompass a photoacid generator (PAG).
• PAG photoacid generator
• HFANB norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol
• NBEtCOOH 3-(bicyclo[2.2.1]hept-2-en-2-yl)propanoic acid
• a negative tone photoimageable composition comprising:
• * w > represents a position at which the bonding takes place with another repeat unit
• R4 is selected from -(CH 2 ) v -C0 2 R4a, -(CH 2 ) v -Ar-OH, -(CH 2 )v-C(0)-Ar-OH,
• « ⁇ ' » represents a position at which the bonding takes place with another repeat unit
• composition of this invention is generally available as a solution.
• the polymer of formula (I), the compounds of formulae (II), (III) and (IV) and one or more PAGs are generally dissolved in one or more solvents. Any of the solvents that would dissolve all of these components to form a homogeneous solution can be employed.
• Exemplary solvents that can be used in the composition of this invention without any limitation maybe selected from the group consisting of: N-methyl-2-pyrrolidone (NMP), ⁇ -butyrolactone (GBL), N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), diethyleneglycol dimethylether, diethyleneglycol diethylether, diethyleneglycol dibutylether, propyleneglycol monomethylether (PGME), dipropylene glycol monomethylether, propyleneglycol monomethylether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl ethyl ketone (MEK), methyl amyl ketone (MAK), cyclohexanone, tetrahydrofuran, methyl- 1 ,3-butyIeneglycolacetate, 1,3- butyleneglycol-3-monomethylether, methyl pyruvate, e
• the coated substrate is heated to facilitate the removal of residual casting solvent, for example to a temperature from 70°C to 130°C for from 1 to 30 minutes, although other appropriate temperatures and times can be used.
• the film is generally imagewise exposed to an appropriate wavelength of actinic radiation, wavelength is generally selected based on the choice of the photoactive compound and/or photosensitizer incorporated into the composition as described herein. However, generally such appropriate wavelength is from 193 to 700 nm. It will be understood that the phrase "imagewise exposure" means exposing through a masking element to provide for a resulting pattern of exposed and unexposed portion of the film.
• the development process generally utilizes an aqueous or an organic solvent developer.
• Suitable aqueous developers include solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and aqueous solutions of organic alkalis such as 0.26N tetramethylammonium hydroxide (TMAH), ethylamine, triethylamine and triethanolamine.
• TMAH tetramethylammonium hydroxide
• ethylamine ethylamine
• triethylamine triethanolamine
• Aqueous solutions of TMAH are well known developer solutions in the semiconductor industry.
• Suitable developers can also include organic solvents such as propylene glycol monomethyl ether acetate (PGMEA), di(propylene glycol) methyl ether acetate (DIPGMEA), 2-heptanone, cyclohexanone, toluene, xylene, ethyl benzene, mesitylene and butyl acetate, and a mixture in any combination thereof, among other suitable solvents.
• organic solvents such as propylene glycol monomethyl ether acetate (PGMEA), di(propylene glycol) methyl ether acetate (DIPGMEA), 2-heptanone, cyclohexanone, toluene, xylene, ethyl benzene, mesitylene and butyl acetate, and a mixture in any combination thereof, among other suitable solvents.
• image fixing is generally accomplished by causing a reaction within the remaining portions of the film.
• Such reaction is generally a cross-linking reaction that can be initiated by heating and/or non-imagewise or blanket exposure of the remaining material.
• the blanket exposure is generally performed using the same energy source as employed in the imagewise exposure although any appropriate energy source can be employed.
• the heating is generally carried out at a desirable temperature, for example, from above 1 10 °C for a time of from 40 min to one or more hours.
• Specific applications of such embodiments encompass a die-attach adhesive to form a single or multilayer semiconductor device, dielectric film which is formed on a semiconductor device; a buffer coat film which is formed on the passivation film; an interlayer insulation film which is formed over a circuit formed on a semiconductor device.
• compositions of this invention can be used to form adhesive layers for bonding the semiconductor chips to each other, such as in chip-stack applications.
• a bonding layer used for such a purpose is composed of a cured product of the adhesive composition of the present invention.
• the adhesive layer is generally a single-layer structure, it should provide sufficient adhesiveness to the substrate and should be free of significant stress resulting due to the curing step. Accordingly, it is now possible to avoid undesirably thick layer of film encompassing the chip as a laminate.
• the laminates formed in accordance with the present invention are reliable in that the relaxation of stress concentration between layers caused by thermal expansion difference or the like can be obtained.
• the semiconductor device having low height and high reliability can be obtained. That is, devices with low aspect ratio and low thickness can be obtained.
• Such semiconductor device becomes particularly advantageous to electronic equipment, which has very small internal volume and is in use while carrying as a mobile device, for example.
• the electronic and/or the semiconductor device according to this invention encompass a laminated semiconductor element where said lamination consists of a composition according to the present invention.
• the developing in accordance with the method of this invention can be performed by any of the known developing techniques such as by the use of an aqueous base solution such as TMAH or an organic solvent as described herein.
• Anhydrous ethyl acetate (132 g) was airlessly added to the pressure cylinder to dissolve the Pd catalyst.
• the solution in the reactor was heated to 70 °C under a nitrogen atmosphere.
• the catalyst solution was then transferred to the heated reaction mixture.
• the syringe pump containing MeOAcNB was started and monomer was added to the reactor according to a predetermined schedule: 0.733 g min for 28 minutes, 0.262 g/min for 78 minutes, 0.190 g/min for 108 minutes, 0.159 g/min for 128 minutes, 0.134 g/min for 153 minutes, 0.106 g/min for 194 minutes, 0.078 g/min for 264 minutes and 0.068 g/min for 303 minutes.
• Patent No. 8,753,790 discloses
• FIG. 1 shows optical micrograph of the images formed from the composition of Example 8, which contained PHS as a polymer containing the repeat units of formula (I) and NBEtOEtNB, a representative compound of formula (II). It is quite evident from this micrograph that excellent negative tone images are observed with no film thickness loss after TMAH development. From FIG. 1 it is also evident that the minimum feature size of the images is at least about 5 micron.
• FIG. 2 similarly shows excellent images can be formed from the composition of Example 9, where PHS was again employed as the polymer containing the repeat units of formula (I) and NBCH 2 OCH 2 OCH2NB, another representative compound of formula (II).
• the developer used was also TMAH.
• the image resolution was again around 5 microns as summarized in Table 3.
• FIG.4 shows optical micrograph of the images formed from the composition of Example 12, which contained a polymer of Example 3 as polymer containing the repeat units of formula (I) and diallyl phthalate as another representative compound of formula (II). It is again evident from this micrograph that good negative tone images are observed with no film thickness loss after TMAH development. From FIG. 4 it is also evident that the minimum feature size of the images is at least about 15 micron.
• FIG. 5 shows optical micrograph of the images formed from the composition of Example
• FIG. 6 shows optical micrograph of the images formed from the composition of
• Example 14 which contained PHS as polymer containing the repeat units of formula (I) and NBPhOAc as another representative compound of formula (IV). It is again evident from this micrograph that negative tone images are observed with some film thickness loss (39%) after TMAH development. From FIG. 6 it is also evident that the minimum feature size of the images is at least about 3 micron.

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• 2017
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