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
  • G03F7/039—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
  • G03F7/0045—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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less

Definitions

• the present disclosure relates to positive photosensitive resin compositions suitable for use in microelectronic applications. More particularly, the present disclosure relates to a chemically amplified, positive working photosensitive polybenzoxazole (PBO) precursor composition and a process for preparing heat- resistant relief structures using the polybenzoxazole precursor photosensitive composition.
• PBO positive working photosensitive polybenzoxazole
• PBO polymers are used as stress buffer coatings and as interlayer dielectric materials in the fabrication of microelectronic devices and packages.
• Stress buffer coatings are coatings applied as the top layer of microelectronic devices such as memory chips in order to mitigate stress related reliability problems in the function of packaged devices.
• interlayer dielectric materials PBO polymer layers function as dielectric coatings that provide electrical isolation between metallic conductors that are located in the same wiring plane, between wiring planes located above or below the PBO layer, or between metallic conductors passing through the PBO layer that are connected to metallic conductors positioned above or below the PBO layer.
• microelectronic lithography processes require reproducible performance from photoimageable materials.
• Photospeed as measured by the energy dose needed for optimal processing, is one of the important lithography parameters requiring a high degree of reproducibility.
• the coating composition must have a high degree of batch-to-batch photospeed reproducibility.
• the present disclosure relates to a positive tone photosensitive composition including:
• R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 1 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C 30 tertiary aminoalkyl, a C 2 -C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C 6 -C 30 substituted or unsubstituted aryl, and a C 1 -C 30 alkyl group containing at least one ether linkage;
• R 30 is a hydrogen atom
• R 31 and R 32 are independently selected from the group consisting of a C3-C3 0 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C 30 tertiary aminoalkyl, a C3-C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C 6 -C 30 substituted or unsubstituted aryl, and a C 3 - C 30 alkyl group containing at least one ether linkage, provided that R 31 and R 32 have at least two substituents on the carbon directly bonded to the nitrogen;
• R 47 is a hydrogen atom, a CrC 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C ⁇ -Cio substituted or unsubstituted aryl; R 48 , R 49 , R 50 , R 51 .
• R 52 , R 53 , R 54 , and R 55 are, independently, a hydrogen atom, a CrC 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C ⁇ -C-io substituted or unsubstituted aryl; J is an oxygen atom, a sulfur atom, or a NR 56 group in which R 56 is a hydrogen atom, a CrC ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl, or a C ⁇ -CI O substituted or unsubstituted aryl; a and b are independently 1 , 2, or 3; and c is 0 or 1 ;
• L is an oxygen atom, a sulfur atom, NR 67 , or CR 69 R 70
• R 67 is a hydrogen atom, a CrC ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl, a C ⁇ -Cio substituted or unsubstituted aryl, or together with R 68 forms a second bond between L and the carbon to which it is attached
• R 69 and R 70 are independently a hydrogen atom, a CrC ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl, or a C ⁇ -Cio substituted or unsubstituted aryl
• R 5 ⁇ R 66 are independently a hydrogen atom, a Ci-C ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl, or a Ce- C 10 substituted or unsubstituted aryl
• R 68 is a hydrogen atom or together
• composition is a chemically amplified composition; provided that when the basic compound is a tertiary amine of Structure XIV, the number of carbon atoms in the basic compound is at least 6 and not all of R 30 , R 31 , and R 32 are a C ⁇ - C30 substituted or unsubstituted aryl.
• chemically amplified composition generally refers to a composition that, upon irradiation with a suitable actinic ray, produces a suitable amount of an acid that catalyzes a deprotection reaction of the photosensitive polymer contained therein so that the solubility of the composition in an aqueous base is modified (e.g., increased).
• a group e.g., alkyl defined by a certain carbon number range (e.g., C 1 -C 30 ) mentioned herein includes all of the species having a carbon number within that range.
• a CrC ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl includes all of the substituted or unsubstituted linear, branched, cyclic alkyl groups having one, two, three, four, five, or six carbon atoms.
• the present disclosure relates to a film including or derived from an above-described composition.
• the present disclosure relates to an article that includes a substrate and an above-described film supported by the substrate.
• the present disclosure relates to a method that includes treating an above-described composition on a substrate to form a relief pattern on the substrate and an article prepared by this method.
• the polybenzoxazole precursor polymer has
• Ar 1 is a tetravalent aromatic group, a tetravalent heterocyclic group, or mixtures thereof;
• Ar 2 is a divalent aromatic, a divalent heterocyclic, a divalent alicyclic, or a divalent aliphatic group that may contain silicon;
• Ar 3 is a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, or mixtures thereof;
• Ar 4 is Ar 1 (OB) k 3 (OH) k 4 or Ar 2 ;
• x is an integer from about 4 to about 1000, y is an integer from 0 to about 500, provided that (x+y) ⁇ 1000;
• B is an acid sensitive group R 1 or a moiety E-O-R 2 containing an acid sensitive group R 2 ;
• E is a divalent aromatic, aliphatic or heterocyclic group which is not acid labile and makes an -E- OH moiety an aqueous base solubilizing group, k 3 is
• the composition further includes a tertiary amine of Structure XIV, in which R 30 , R 31 , and R 32 are C 6 -C 30 substituted or unsubstituted aryl (e.g., phenyl).
• the composition further includes an adhesion promoter.
• the adhesion promoter can include a compound selected from the group consisting of vinylalkoxysilanes, methacryloxalkoxysilanes, mercaptoalkoxysilanes, epoxyalkoxysilanes and glycidoxyalkoxysilanes.
• the composition further includes a solvent.
• the uncured film has a thickness of at least about 4 ⁇ m. In a preferred embodiment the uncured film thickness is at least about 6 ⁇ m. In a more preferred embodiment the uncured film thickness is at least about 8 ⁇ m.
• the substrate includes a wafer, such as a silicon wafer, a ceramic wafer, a gallium arsenide wafer, an indium phosphide wafer, a glass wafer, a metal wafer, or a plastic wafer.
• the wafer is a metal coated wafer.
• the method further includes applying the composition to the substrate prior to treating the composition.
• treating the composition includes baking the composition to form a baked composition.
• treating the composition can further include exposing the baked composition to actinic radiation to form an exposed composition, developing the exposed composition with an aqueous developer, thereby forming an uncured relief image on the substrate, and curing the relief image.
• the photosensitive composition may contain other additives, which may include, but are not limited to, photosensitizers, surfactants, dyes, adhesion promoters, and leveling agents.
• additives may include, but are not limited to, photosensitizers, surfactants, dyes, adhesion promoters, and leveling agents.
• the present disclosure also relates to the process for preparing heat- resistant relief structures from the aforementioned positive working photosensitive composition and the articles of manufacture obtained by the combination of the composition and the method of use according to the disclosure.
• the heat resistant positive working photosensitive composition can be coated on a substrate to create a film, which can then be subjected to patterning through a photolithographic process. After photolithographic processing, the patterned film can be converted to a heat resistant polybenzoxazole relief image by application of additional heat.
• the photosensitive resin compositions can be used as stress buffer coatings, alpha particle barrier films, interlayer dielectrics, and patterned engineering plastic layers in the manufacturing of microelectronic devices.
• photoimageable coating compositions that use photochemically generated acids to effect the operation of the imaging chemistry can be susceptible to unacceptable variation in batch-to-batch photospeed due to the presence of small amount of basic impurities that neutralize a portion of the photochemically generated acid before the acid can initiate the imaging chemistry process.
• This disclosure describes a strategy for removing this variation by formulating the coating composition in a manner that achieves a constant amount of total base in the composition.
• a positive working photosensitive composition e.g., a chemically amplified positive working photosensitive composition
• small amounts of certain basic compounds and PBO precursors blocked with different moieties e.g., a chemically amplified positive working photosensitive composition
• compositions with high batch-to-batch photospeed reproducibility The presence of the basic compound surprisingly slows down the photospeed of these compositions, thereby resulting in compositions with high batch-to-batch photospeed reproducibility.
• the inventors also surprisingly discovered that presence of a small amount of base in positive working photosensitive PBO compositions can greatly improve shelf life of these compositions, and remove chemical undercut of a film made by these compositions (e.g., in the presence of a certain adhesion promoter such as an epoxy adhesion promoter).
• chemical undercut mentioned herein generally refers to loss of a portion of the bottom of a film (e.g., a portion along the interface between the film and a substrate) during a lithographic process.
• the present disclosure relates to a positive tone photosensitive composition containing: (a) at least one polybenzoxazole precursor polymer having Structure I or Il or II *
• Ar 1 is a tetravalent aromatic group, a tetravalent heterocyclic group, or mixtures thereof
• Ar 2 is a divalent aromatic, a divalent heterocyclic, a divalent alicyclic, or a divalent aliphatic group that may contain silicon, or mixtures thereof
• Ar 3 is a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, or mixtures thereof
• Ar 4 is Ar 1 (OB) k 3 (OH) k 4 or Ar 2
• x is an integer from about 4 to about 1000
• y is an integer from 0 to about 500, provided that (x+y) ⁇ 1000
• B is an acid sensitive group R 1 or a moiety E-O-R 2 containing an acid sensitive group R 2
• E is any suitable divalent aromatic, aliphatic or heterocyclic group which is not acid labile and makes an -E-OH moiety an aqueous base solubilizing group
• k 3 is a
• Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 1 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 30 tertiary aminoalkyl, a C 2 -C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C 6 -C 30 substituted or unsubstituted aryl, and a C 1 -C 3 Q alkyl group containing at least one ether linkage;
• secondary amines of Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 1 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 30 tertiary aminoalkyl, a C 2 -C 30 substituted or unsubstituted linear,
• R 30 is a hydrogen atom
• R 31 and R 32 are independently selected from the group consisting of a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 30 tertiary aminoalkyl, a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a Ce-C 30 substituted or unsubstituted aryl, and a C 3 - C 30 alkyl group containing at least one ether linkage, provided that R 31 and R 32 have at least two substituents on the carbon directly bonded to the nitrogen; (3) cyclic amines of Structure XVI:
• R 47 is a hydrogen atom, a d-C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C 6 -C 1 0 substituted or unsubstituted aryl; R 48 , R 49 , R 50 , R 51 .
• R 52 , R 53 , R 54 , and R 55 are, independently, a hydrogen atom, a C 1 -C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C 6 -C 10 substituted or unsubstituted aryl;
• J is an oxygen atom, a sulfur atom, or a NR 56 group in which R 56 is a hydrogen atom, a C 1 -C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C 6 -CiO substituted or unsubstituted aryl;
• a and b are independently 1 , 2, or 3; and c is 0 or 1 ;
• L is an oxygen atom, a sulfur atom, NR 67 , or CR 69 R 70
• R 67 is a hydrogen atom, a C 1 -C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 6 -C 1O substituted or unsubstituted aryl, or together with R 68 forms a second bond between L and the carbon to which it is attached
• R 69 and R 70 are independently a hydrogen atom, a C 1 -C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C 6 -C 10 substituted or unsubstituted aryl
• R 5 ⁇ R 66 are independently a hydrogen atom, a C 1 -C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C 6 - Cio substituted or unsubstituted aryl;
• tertiary alicyclic amines (5) tertiary alicyclic amines; and (6) quaternary ammonium hydroxides, provided that when the basic compound is a tertiary amine of Structure XIV, the number of carbon atoms in the basic compound is at least 6 and not all of R 30 , R 31 , and R 32 are a C 6 -C 3 O unsubstituted aryl.
• the photosensitive composition may also contain other additives, which may include, but are not limited to, photosensitizers, surfactants, dyes, adhesion promoters, and leveling agents and a solvent.
• additives may include, but are not limited to, photosensitizers, surfactants, dyes, adhesion promoters, and leveling agents and a solvent.
• the PBO precursor polymers are synthesized employing a multi-step synthetic process.
• the first step in preparation of the PBO precursor polymers of Structure I, Il or II* bearing acid labile functional groups is to produce the PBO precursor base polymer of Structure III:
• Ar 1 , Ar 2 , and Ar 3 are as defined previously and Ar 4 is Ar 1 (OH) 2 or Ar 2 .
• the polymers of Structure III can be prepared from the reaction of monomers having structure Vl with one or more monomers of structure IV and optional amount of monomers having structure V in the presence of a base.
• W is selected from the group consisting of a carboxylic acid group, a carboxylic acid ester group, an acid halide group and an acid anhydride group.
• Ar 1 is a tetravalent aromatic group or a tetravalent heterocyclic group, or mixtures thereof.
• Ar 1 include, but are not limited to:
• X 1 is -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO- or -SiR 1 V and each R 13 is independently a Ci - C 7 linear or branched alkyl, a C 5 - C 8 cycloalkyl group or a subtituted or unsubstituted C6-C 20 aryl group.
• R 13 examples include, but are not limited to, -CH 3 , -C 2 H 5 , /7-C 3 H 7 , /-C 3 H 7 , H-C 4 H 9 , f-C 4 H 9 , cyclohexyl, phenyl, methylphenyl, and naphthyl.
• a mixture of monomers of Structure IV with the same or different Ar 1 groups may be employed.
• Examples of monomers having Structure IV containing Ar 1 include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'- dihydroxy-4,4'-diaminodiphenylether, 3,3'-dihydroxybenzidine, 4,6-diaminoresorcinol, and 2,2-bis(3-amino-4-hydroxyphenyl)propane.
• the substitution pattern of the two hydroxy and two amino groups in the monomer of Structure IV may be any of the possible substitution patterns with the proviso that the each amino group has an ortho relationship with a hydroxyl group in order to be able to form the benzoxazole ring.
• polybenzoxazole precursor base polymer of Structure I may be synthesized using a mixture of two or more monomers described by generic Structure IV.
• Ar 2 is a divalent aromatic, a divalent heterocyclic, a divalent alicyclic, or a divalent aliphatic group that may contain silicon. Examples of Ar 2 include, but are not limited to,
• X 2 is -O-, -S-, -C(CFa) 2 -, -C(CH 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO- or -SiR 1 V and each R 14 is independently a Ci - C 7 linear or branched alkyl or a C 5 - C 8 cycloalkyl group or a subtituted or unsubstituted C 6 -C 20 aryl group, X 3 is -O-, -S-, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -CH 2 -, -SO 2 -, or -NHCO-, Z is hydrogen atom, a Ci - C 8 linear, branched or cyclic alkyl, or a C ⁇ -Cio aryl group and p is an integer from 1 to 6.
• suitable Z groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n- butyl, sec-butyl, f-butyl, n-octyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, methylphenyl and cyclooctyl.
• R 14 include, but are not limited to, -CH 3 , -C 2 H 5 , n-C 3 H 7 , /-C 3 H 7 , H-C 4 H 9 , NC 4 H 9 , cyclohexyl, phenyl, methylphenyl, and naphthyl.
• Examples of monomers having the Structure V containing Ar 2 include, but are not limited to, 5(6)-diamino-1-(4-aminophenyl)-1 ,3,3-trimethylindane, m- phenylenediamine, p-phenylenediamine, 2 I 2'-bis(trifluoromethyl)-4,4'-diamino-1 , 1 '- biphenyl, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'- diaminodiphenyl ether, 2,4-toluenediamine, 3,3'-diaminodiphenyl sulfone, 3,4'- diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'- diaminodiphenylmethane, 3,4'-diaminodiphenylme
• Ar 3 is a divalent aromatic, a divalent aliphatic, or a divalent heterocyclic group.
• Examples of Ar 3 include, but are not limited to:
• X 4 is -O-, -S-, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -CH 2 -, -SO 2 -, or -NHCO-.
• W is typically C(O)CI, COOH, C(O)OR 20 ,
• R 20 is a Ci-C 7 linear or branched alkyl group, a C 5 - C 8 cycloalkyl group or a phenyl group optionally substituted with one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or halo groups.
• R 20 examples include, but are not limited to, -CH 3 , -C 2 H 5 , n-C 3 H 7 , /-C 3 H 7 , H-C 4 H 9 , f-C 4 H 9 , phenyl, toluyl, dimethylphenyl, chlorophenyl, fluorophenyl, and cyclohexyl.
• Monomers having the Structure Vl are diacids, diacid dichlorides, diacid anhydrides and diesters.
• Suitable diacid chlorides include, but are not limited to, isophthaloyl dichloride, phthaloyl dichloride, terephthaloyl dichloride, 1 ,4-oxydi benzoyl chloride, adipoyl chloride, 1,4-cyclohexyldicabonyl dichloride and mixtures thereof.
• diacid dianhydrides include but not limited to isophthalic-acetic dianhydride, terphthalic-triflic dianhydride, isophthalic-methanesulfonic dianhydride, 1 ,4-oxydibenzoic -p-toluenesulfonic acid dianhydride and terphthalic- acetic dianhydride.
• Suitable dicarboxylic esters include, but are not limited to, dimethyl isophthalate, dimethyl phthalate, dimethyl terephthalate, diethyl isophthalate, diethyl phthalate, diethyl terephthalate, diethyl succinate, dimethyl adipate and mixtures thereof.
• Any conventional method for reacting a dicarboxylic acid or its dichloride, diester or dianhydride with at least one aromatic and/or heterocyclic dihydroxydiamine, and optionally, with at least one diamine may be used.
• Suitable amine bases include, but are not limited to, pyridine, triethylamine, 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU), 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN), dimethylpyridine, and dimethylaniline.
• DBU 1,8- diazabicyclo[5.4.0]undec-7-ene
• DBN 1,8- diazabicyclo[4.3.0]non-5-ene
• dimethylpyridine dimethylaniline
• the polybenzoxazole precursor base polymer of Structure III may be isolated by precipitation into water, recovered by filtration and dried. Dianhydride synthesis may be carried out under similar conditions. Descriptions of suitable syntheses employing diesters or diacids may be found in US Patent Nos. US 4,395,482, US 4,622,285, and US 5,096,999, herein incorporated by reference.
• the preferred reaction solvents are N-methyl-2-pyrrolidone (NMP), N- ethyl-2-pyrrolidone (NEP), gamma-butyrolactone (GBL), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone, dimethylsulfoxide (DMSO), sulfolane, and diglyme.
• NMP N-methyl-2-pyrrolidone
• NEP N- ethyl-2-pyrrolidone
• GBL gamma-butyrolactone
• DMF N,N-dimethylformamide
• DMAc N,N-dimethylacetamide
• dimethyl-2-piperidone dimethylsulfoxide
• sulfolane and diglyme.
• the most preferred solvents are N-methyl-2- pyrrolidone (NMP) and gamma- butyrolactone (GBL).
• Monomers having Structure IV, V, and Vl are employed such that the ratio of [IV + VJA/I is generally from about 1 to about 1.2. Preferably, the ratio of [IV + V]/VI is generally from about 1 to about 1.1.
• the monomer having the Structure IV is employed from about 50 to about 100 mole % of [IV + V) and the monomer having Structure V is employed from about 0 to about 50 mole % of [IV + V].
• Distribution of the polymeric units resulting from monomers having the Structures IV and V in the polybenzoxazole precursor base polymer of Structure I may be random or in blocks.
• x is an integer from about 4 to about 1000
• y is an integer from about 0 to about 500 and (x+y) is less than about 1000.
• a preferred range for x is from about 6 to about 300 and a preferred range for y is from about 0 to about 50.
• a more preferred range for x is from about 10 to about 100 and a more preferred range for y is from about 0 to about 10.
• the most preferred range for x is from about 10 to about 50 and a most preferred range for y is from about 0 to about 5.
• the amount of y is always less than x in order for the polymers of Structure III, VII, and VII* (vide infra) to be aqueous base soluble.
• a preferred range for the ratio of y/x is from 0 to 50/100.
• a more preferred range for the ratio of y/x is from 0 to 25/100.
• a most preferred range for the ratio of y/x is from 0 to 10/100.
• aqueous base solubility is defined to mean the ability of a film to dissolve at a rate of at least 2 microns per minute in an aqueous base developer (vide infra) having a pH within the range of from about 9 to about 12.
• the amount of (x+y) (also referred to as the degree of polymerization) can be calculated by dividing the numeric average molecular weight (Mn) of a polymer of Structure I by the average molecular weight of the repeat unit.
• Mn can be determined by such standard methods as membrane osmometry or gel permeation chromatography as described, for example, in Jan Rabek, Experimental Methods in Polymer Chemistry, John Wiley & Sons, New York, 1983.
• molecular weight and inherent viscosity of the polymers can have a wide range depending on the reaction conditions chosen and considerations such as the purity of the solvent, the humidity, presence or absence of a blanket of nitrogen or argon gas, reaction temperature, reaction time, and other variables.
• Ar 1 , Ar 2 , and Ar 3 are as defined previously and Ar 4 is Ar 1 (OH) 2 or Ar 2 ;
• G is a monovalent organic group having a carbonyl, carbonyloxy or sulfonyl group attached directly to the terminal NH of the polymer, which may be further substituted by other functional groups such as vinyl, carbonyl, ether ester, or carboxylic acids,
• G* is a substituted or unsubstituted divalent organic group having at least one carbonyl or sulfonyl group attached directly to the terminal N of the polymer; and M is a reactive leaving group.
• G examples include, but are not limited to, the following structures:
• M groups include, but are not limited to Cl, Br, mesylate, triflate, substituted carbonyloxy groups, and substituted carbonate groups.
• G-M compounds include but are not limited to, carboxylic and sulfonic acid chlorides, carbon and sulfonic acid bromides, linear and cyclic carbon and sulfonic acid anhydrides, and alkoxy or aryloxy substituted acid chlorides.
• G-M compounds include maleic anhydride, succinic anhydride, acetic anhydride, propionic anhydride, norbomene anhydride, phthalic anhydride, camphor sulfonic acid anhydride, trifluoromethane sulfonic acid anhydride, methanesulfonic acid anhydride, p-toluenesulfonic acid anhydride, ethanesulfonic acid anhydride, butanesulfonic acid anhydride, perfluorobutanesulfonic acid anhydride, acetyl chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, benzoyl chloride, norbornene carboxylic acid chloride, di-f-butyl dicarbonate, dimethyl dicarbonate, diethyldicarbonate, dibutyldicarbonate, f-butyl chloroformate, ethyl chloroformate,
• the reaction can be carried out in a suitable solvent by addition of G-M to a dry solution of the polybenzoxazole precursor base polymer of Structure I at a temperature from about -25 0 C to about 7O 0 C.
• the more preferred temperature is from about O 0 C to about 6O 0 C.
• the most preferred temperature is from about 5 0 C to about 55 0 C.
• the reaction time is from about 1 hour to about 24 hours.
• the molar amount of G-M employed is a slightly excess (3-6%) of the sum of the molar amounts of the monomer of Structures IV and V less the molar amount of monomer of Structure Vl. Addition of organic or inorganic base may also be employed.
• Suitable organic amine bases include, but are not limited to, pyridine, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non- 5-ene (DBN), dimethylpyridine, and dimethylaniline.
• suitable bases include sodium hydroxide, sodium carbonate, and sodium silicate.
• the preferred reaction solvents are propylene glycol methyl ether acetate (PGMEA), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), gamma-butyrolactone (GBL), N,N-dimethylformamide (DMF), N 1 N- dimethylacetamide (DMAc), dimethyl-2-piperidone, dimethylsulfoxide (DMSO), tetrahydrofuran (THF), acetone, sulfolane, and diglyme.
• the most preferred solvents are diglyme and PGMEA.
• the endcapping reaction with certain endcapping reagents may not stop after the endcapping reaction.
• a subsequent dehydration step may also occur to form a divalent endcap (G* in Structures II * and VII*).
• Ar 1 , Ar 2 , and Ar 3 are as defined previously and Ar 4 is Ar 1 (OH) 2 or Ar 2 .
• Ar 4 is Ar 1 (OH) 2 or Ar 2 .
• a typical reaction between an amine end group and a cyclic anhydride endcapping reagent is shown below.
• cyclic anhydrides which may undergo this additional reaction include, but are not limited to, maleic anhydride, succinic anhydride, norbornane anhydride, norbornene anhydride, itaconic anhydride, camphor anhydride, and the compounds shown below.
• Ar 1 , Ar 2 , Ar 3 , , x, y, k 3 , k 4 , G and G* are as defined as above;
• Ar 4 is Ar 1 (OB) k 3 (OH) k 4 or Ar 2 ,
• B is an acid sensitive group R 1 or a moiety E-O-R 2 containing an acid sensitive group R 2 .
• the term "acid sensitive group” refers to a group that is capable of reacting with an acid (e.g., to form an aqueous base solubilizing group) under a suitable condition (e.g., during heating in a lithographic process).
• suitable R 1 groups include, but are not limited to,
• R 1 in combination with the O atom attached to the Ar 1 group forms groups such as acetal groups, ketal groups, ether groups, carbonate groups and silyl ethers groups.
• Mixtures of R 1 groups may be employed.
• PBO precursor polymers having a mixture of R 1 groups, R 2 groups, or R 1 and EOR 2 groups may be employed.
• the ratios of different R 1 groups, R 2 groups, or R 1 and EOR 2 groups may range from 9:1 to 1 :9.
• the ratios of different R 1 groups, R 2 groups, or R 1 and EOR 2 groups range from 8:2 to 2:8. More preferably, the ratios of different R 1 groups, R 2 groups, or R 1 and EOR 2 groups range from 7:3 to 3:7.
• the ratios of different R 1 groups, R 2 groups, or R 1 and EOR 2 groups range from 6:6 to 4:6.
• R 1 groups are those groups which in combination with the O atom attached to Ar 1 form acetal groups. More preferred R 1 groups include, but are not limited to:
• E is any suitable divalent aromatic, aliphatic or heterocyclic group which is not acid labile (i.e., chemically inert to an acid) and makes an -E-OH moiety that is an aqueous base solubilizing moiety (i.e., a moiety that enables a compound having the moiety to be soluble in an aqueous base, e.g., an aqueous base commonly used in a lithographic process).
• R 2 is any acid labile group.
• the preferred -E-OH are phenols or aromatic or aliphatic carboxylic acids. Examples of the E group include, but are not limited to, the following structures
• E-O-R include but are not limited to, the following structures:
• R 2 in combination with a portion of E, forms groups such as acetal groups, ketal groups, ether groups, silyl ethers groups, acid sensitive methylene ester groups (e.g. methylene f-butyl ester group), acid sensitive ester groups and carbonates. Mixtures of E and R 2 groups may be employed.
• R 1 and R 2 are low activation energy groups (e.g. acetals), it is preferred that G not be derived from cyclic anhydrides, although G* may be.
• Preferred E-O-R 2 groups are those, containing acetals or acid sensitive esters. More preferred E-O-R 2 groups include, but are not limited to:
• the reaction of the OH groups in monomeric units in the PBO precursor polymers of Structures III, VII and VII* (resulting from monomers of Structure IV) to generate acid sensitive groups B may be accomplished in different ways depending on which acid sensitive moiety is employed or if the spacer group E is employed.
• the acid sensitive, end capped PBO precursor of Structure I may be prepared by an acid catalyzed addition reaction of vinyl ethers with Structure III in a process similar to the one described in US Patent No. 6143467 and US Patent No. 7132205.
• Any suitable acid catalyst may be used for the reaction, for example, hydrochloric acid, p-toluene sulfonic acid and pyridinium-p- toluene sulfonate.
• the acid catalyst may be added in amounts ranging from 0.001 wt% to about 3.0 wt%.
• vinyl ethers with a range of activation energies towards acid induced deprotection can be used in this reaction.
• the examples of such vinyl ethers include but are not limited to ethyl vinyl ether, f-butyl vinyl ether, vinyl cyclohexyl ether, 2-ethylhexyl vinyl ether, dihydrofuran, 2-methoxy-1-propene, and dihydropyran. Structures VII or VII* may be reacted similarly to produce Il and II * .
• the preparation of PBO precursor polymers having a mixture of R 1 groups can be produced by using a mixture of vinyl ethers.
• PBO precursors polymers of Structures I, Il and II* useful in this disclosure may also be prepared using a process consisting of the acid catalyzed reaction of a PBO precursor polymer of Structures III, VII or VII*, f-butyl vinyl ether and an alkyl-, alkylene-, cycloalkyl-, cycloalkylalkyl or arylalkyl alcohol as described for polymers derived from hydroxystyrene in US Patent No. 6,133,412, herein incorporated by reference.
• R 3 include, but are not limited to substituted or unsubstituted linear, branched or cyclic alkyl groups preferably having 1 to 18 carbon atoms, substituted or unsubstituted linear, branched or cyclic halogenated alkyl groups preferably having 1 to 18 carbon atoms, or arylalkyl groups.
• R 4 and R 5 groups include, but are not limited to, hydrogen, linear, branched, or cyclic alkyl groups, linear or branched alkylene group bearing a cycloalkyl substituent, substituted cycloalkyl, aryl, and substituted aryl groups, preferably having 1 to 10 carbon atoms.
• Structures I, Il and II * bearing acid labile functional groups is from the reaction of the PBO precursor of Structure III, VII, or VII* with f-butyl (or other tertiary acid sensitive group) bromoacetate in the presence of base as described for polymers containing hydroxystyrene units in US Patent No. 5,612,170.
• Benzyl bromides bearing acid sensitive substituents e.g. f-butyl esters, carbonates, or alpha alkoxy esters
• SiIyI group protected PBO precursor polymers of Structures I, Il and M* may be prepared similarly by reacting the polymer with silyl halides under basic conditions.
• Ether (e.g. f-butyl) protected PBO precursor polymers of Structures I 1 II and II* may be prepared using standard synthetic procedures for the conversion of alcohol groups to ether groups.
• the preparation of PBO precursor polymers having a mixture of R 2 groups can be produced by using a mixture of the corresponding reactants used for the corresponding R 2 .
• the reactants may be used as a mixture, reacted sequentially in the same reaction pot, or reacted in consecutive reactions.
• the preparation of PBO precursor polymers having a mixture of R 1 and EOR 2 groups are preferably prepared using 2 consecutive reaction steps with the synthesis step attaching R 1 being carried out first.
• PBO precursor polymers of this disclosure have a k 3 from about 0.1 to about 2.
• a preferred value for k 3 is from about 0.1 to about 1.5.
• a more preferred value for k 3 is from about 0.2 to about 1.2.
• the most preferred value for k 3 is from about 0.3 to about 0.8.
• the corresponding values for k 4 are 2-k 3 .
• k 3 is calculated by determining, using analytical methods, the percentage of OH groups attached to Ar 1 that have been reacted and then multiplying that percentage by 0.02.
• the positive-working formulation of the present disclosure uses one or more compounds which release acid upon exposure to radiation.
• Such materials are commonly called PhotoAcid Generators (PAGs).
• PAGs used in the present disclosure are preferably active to the radiation between about 300 nm to about 460 nm. They should form a homogeneous solution in the photosensitive composition and produce strong acid upon irradiation. Examples of such strong acids include hydrogen halides or a sulfonic acid.
• the classes of such PAGs include, but are not limited to, oxime sulfonates, triazines, diazoquinone sulfonates, aromatic sulfonyl imides or sulfonium or iodonium salts of sulfonic acids. Examples of suitable PAGs include but are not limited to:
• R 6 and R 7 are each independently linear, branched or cyclic alkyl or aryl group containing 1 to 20 carbon atoms and X " is R 15 SOa " (R 15 is a substituted or unsubstituted, linear, branched or cyclic C 1 -C 25 alkyl or an single or multinuclear aryl group having a total of from 6 to 25 carbons); R 8 , R 9 , R 10 and R 11 are independently linear, branched or cyclic alkyl groups and R 12 is a linear or branched CrC 8 alkyl, C 5 - C 8 cycloalkyl, camphoroyl or toluyl; R 90 is C 1 -C 8 a linear or branched alkyl that may contain F, or Cs-C 8 cycloalkyl and R 91 is an aromatic group.
• PAGs of the diazoquinone sulfonate class are generally prepared by condensation of the diazoquinone sulfonyl chloride with a wide variety of phenolic compounds known to those skilled in the art including, but not limited to phenol, trihydroxybenzophenone, and those described in US Patents 5541033, 4992596, 6040107, and 5554797 herein incorporated by reference. Specific examples of PAGs include but are not limited to:
• acid could be generated by a combination of
• PAG/sensitizer In such systems energy of radiation is absorbed by the sensitizer and transmitted in some manner to the PAG. The transmitted energy causes PAG decomposition and generation of photoacid.
• Any suitable photoacid generator compound may be used. Suitable classes of photoacid generators generating sulfonic acids include, but are not limited to, sulfonium or iodonium salts, oximidosulfonates, bissulfonyidiazomethane compounds, and nitrobenzylsulfonate esters. Suitable photoacid generator compounds are disclosed, for example, in US- Patent Nos. 5,558,978 and 5,468,589 which are incorporated herein by reference.
• photoacid generators are perfluoroalkyl sulfonyl methides and perfluoroalkyl sulfonyl imides such as those disclosed in US Patent No. 5,554,664, which is incorporated herein by reference.
• photoacid generators include triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, diphenylethylsulfonium chloride, phenacyldimethylsulfonium chloride, phenacyltetrahydrothiophenium chloride, 4-nitrophenacyltetrahydrothiopheniumn chloride, and 4-hydroxy-2-methylphenylhexahydrothiopyrylium chloride.
• photoacid generators for use in this disclosure include triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, methylphenyldiphenylsulfonium perfluorooctanesulfonate, methylphenyldiphenysulfonium perfluorooctanesulfonate, 4-n-butoxyphenyl- diphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4,6-triisopropylbenzenesulfonate, phe ⁇ ylthiophenyldip
• Suitable iodonium salts for use in this disclosure include, but are not limited to, diphenyl iodonium perfluorobutanesulfonate, bis-(t- butylphenyl)iodonium perfluorobutanesulfonate, bis-(f-butylphenyl)iodonium perfluorooctanesulfonate, diphenyl iodonium perfluorooctanesulfonate, bis-(f- butylphenyl)iodonium benzenesulfonate, bis-(f-butylphenyl)iodonium 2,4,6- triisopropylbenzenesulfonate, and diphenyliodonium 4-methoxybenzensulfonate.
• photoacid generators for use in this disclosure are bist ⁇ -toluenesulfonyljdiazomethane, methylsulfonyl p-toluenesulfonyl- diazomethane, 1-cyclo-hexylsulfonyl-1-(1 ,1-dimethylethylsulfonyl)diazomethane, bis(1 ,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, 1 -p-toluenesulfonyl-1 -cyclohexylcarbonyl- diazomethane, 2-methyl-2-(p-toluenesulfony1 )propiophenone, 2-methanesulfon
• sensitizers include but are not limited to: 9- methylanthracene, anthracenemethanol, acenaththalene, thioxanthone, methyl-2- naphthyl ketone, N-ethyl-3,6-bis(benzoyl)-carbazole I 9,9'-ethyl-3,3'-dicarbazolyl, 4- acetylbiphenyl, 1 ,2-benzofluorene, 9,10-dimethoxyanthracene, 9,10-dimethoxy-2- ethylanthracene and 9,10-dibutoxyanthracene.
• compositions of this disclosure in one embodiment further includes a basic compound selected from the group consisting of tertiary amines, hindered secondary amines, non-aromatic cyclic amines and quaternary ammonium provided that when the basic compound is a tertiary amine of Structure XIV, the number of carbon atoms in the basic compound is at least 6 and not all of R 30 , R 31 , and R 32 are a C 6 -C 30 substituted or unsubstituted aryl.
• a non- aromatic amine is defined as an amine in which the N is not part of an aromatic ring.
• a tertiary amine with less than 6 carbons is considered to be too volatile in the lithographic process to obtain reproducible results.
• Suitable tertiary amines are defined by Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a CrC 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 30 tertiary aminoalkyl, a C 2 - C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C 6 -C 30 substituted or unsubstituted aryl, or a CrC 30 alkyl group containing at least one ether linkage, provided that when the basic compound is a tertiary amine of Structure XIV, the number of carbon atoms in the basic compound is at least 6 and not all of R 30 , R 31 , and R 32 are a C 6 -C 30 unsubstituted aryl.
• Examples of Structure XIV include, but are not limited to the following compounds.
• preferred tertiary amines are those tertiary amines described by Structure XIV in which at least one of R 30 , R 31 , and R 32 are a CrC 30 alkyl group containing at least one ether linkage.
• preferred tertiary amines are those tertiary amines described by Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -Ci 5 tertiary aminoalkyl, a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, and a C 6 -C 30 substituted or unsubstituted aryl which are "hindered”.
• Hindered tertiary amines are hereby defined as tertiary amines in which at least two of R 30 , R 31 , and R 32 have at least two substituents on the carbon bonded to the tertiary nitrogen as illustrated in Structure XV, in which R 44 , R 45 , and R 46 are independently selected from the group consisting of hydrogen, a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -Ci 5 tertiary aminoalkyl, a C 3 - C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl and a C 6 -C 30 substituted or unsubstituted aryl in which at least two of R 44 , R 45 , and R 46 are not hydrogen atoms. Two of R 44 , R 45 , and R 46 may be connected to form a ring.
• hindered tertiary amines include, but are not limited to the following compounds.
• the more preferred tertiary amines are those tertiary amines described by Structure XIV in which at least one of R 30 , R 31 , and R 32 are a C 3 -Ci 5 alkyl group containing at least one ether linkage.
• the more preferred tertiary amines are those hindered tertiary amines described by Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 3 -C 15 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -Ci 0 tertiary aminoalkyl, a C 3 -Ci 5 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl and a C 6 -Ci 0 substituted or unsubstituted aryl.
• the most preferred tertiary amines are those tertiary amines described by Structure XIV in which at least two of R 30 , R 31 , and R 32 are a C 3 -C 15 alkyl groups containing at least one ether linkage.
• the most preferred tertiary amines are those hindered tertiary amines described by Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 3 -C 1 Q substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C6 tertiary aminoalkyl, or a C 3 -C 10 substituted or unsubstituted linear, branched or cyclic hydroxyalkyl, and a substituted or unsubstituted phenyl group.
• compositions of this disclosure include as the basic compound a tertiary amine, defined by Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 1 -C30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 30 tertiary aminoalkyl, a C 2 -C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, or a C 1 -C 30 alkyl group containing at least one ether linkage, with the proviso that the number of carbons contained in R 30 , R 31 , and R 32 is at least 6.
• Examples of Structure XIV in this alternate embodiment include, but are not limited to the following compounds.
• preferred tertiary amines are those tertiary amines described by Structure XIV in which at least one of R 30 , R 31 , and R 32 are a C 1 -C 30 alkyl group containing at least one ether linkage.
• preferred tertiary amines are those tertiary amines described by Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -Ci 5 tertiary aminoalkyl, a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, and which are "hindered.”
• Examples of hindered tertiary amines in this alternate embodiment include, but are not limited to the following compounds.
• the more preferred tertiary amines are those tertiary amines described by Structure XIV in which at least one of R 30 , R 31 , and R 32 are a C 3 -Ci 5 alkyl group containing at least one ether linkage.
• the more preferred tertiary amines are those hindered tertiary amines described by Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 3 -Ci 5 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -Ci 0 tertiary aminoalkyl, and a C 3 - Ci 5 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl.
• the most preferred tertiary amines are those tertiary amines described by Structure XIV in which at least two of R 30 , R 31 , and R 32 are a C 3 -C 15 alkyl groups containing at least one ether linkage.
• the most preferred tertiary amines are those hindered tertiary amines described by Structure XIV in which R 30 , R 31 , and R 32 are independently selected from the group consisting of a C3-C 1 0 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 6 tertiary aminoalkyl, and a C 3 -Ci 0 substituted or unsubstituted linear, branched or cyclic hydroxyalkyl.
• Hindered secondary amines are amines defined by Structure XIV in which R 30 is a hydrogen atom and R 31 and R 32 are independently selected from the group consisting of a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 30 tertiary aminoalkyl, a C 3 -C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a Ce-C 30 substituted or unsubstituted aryl, and a C 3 - C 30 alkyl group containing at least one ether linkage and in which R 31 and R 32 have at least two substituents on the carbon bonded to the nitrogen as illustrated in Structure XV.
• hindered secondary amines include, but are not limited to, diphenylamine, dicyclohexylamine, di-t-butylamine, t-butyl-phenylamine, t-butyl- cyclohexylamine, diisopropylamine, di-t-amylamine, phenyl- cyclohexylamine, phenyl-napthylamine, dinaphthylamine, dianthracenylamine, and compounds represented by the following structures.
• Preferred hindered secondary amines are amines defined by Structure
• R 30 is a hydrogen atom and R 31 and R 32 are independently selected from the group consisting of a C 3 -Ci 5 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 20 tertiary aminoalkyl, a C3-C 15 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C 6 -Ci 0 substituted or unsubstituted aryl, and a C 3 -Ci 5 alkyl group containing at least one ether linkage and in which R 31 and R 32 have at least two substituents on the carbon bonded to the nitrogen as illustrated in Structure XV.
• More preferred hindered secondary amines are amines defined by
• R 30 is a hydrogen atom and R 31 and R 32 are independently selected from the group consisting of a C 3 -C 10 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -Ci 0 tertiary aminoalkyl, a C 3 -Ci 0 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a substituted or unsubstituted phenyl group, and a C 3 -C 15 alkyl group containing at least one ether linkage and in which R 31 and R 32 have at least two substituents on the carbon bonded to the nitrogen as illustrated in Structure XV.
• Most preferred hindered secondary amines are amines defined by Structure XIV in which R 30 is a hydrogen atom and R 31 and R 32 are independently selected from the group consisting of a C 3 -Ci 0 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 20 tertiary aminoalkyl, a C 3 -Ci 0 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a substituted or unsubstituted phenyl group and a C 3 -C 15 alkyl group containing at least one ether linkage and in which R 31 and R 32 have at least two substituents on the carbon bonded to the nitrogen as illustrated in Structure XV and at least one of R 31 and R 32 is selected from a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, and a
• Non-aromatic cyclic amines are amines in which the amine nitrogen is incorporated into a primarily carbocyclic ring structure which may contain additional heteroatoms such as oxygen, sulfur, or another nitrogen.
• the ring structure may be monocyclic, bicyclic, or tricyclic, and may contain double bonds.
• classes of non-aromatic cyclic amines include, but are not limited to, amines described by Structures XVI, XVII, and tertiary alicyclic amines.
• R 47 is a hydrogen atom, a CrC 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C 6 -Ci O substituted or unsubstituted aryl; R 48 , R 49 , R 50 , R 51 .
• R 52 , R 53 , R 54 , and R 55 are independently a hydrogen atom, a CrC 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C 6 -C 10 substituted or unsubstituted aryl; J is an oxygen atom, a sulfur atom, or a NR 56 group where R 56 is a hydrogen atom, a Ci-C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C 6 -Ci O substituted or unsubstituted aryl; a and b are independently 1 , 2, or 3 and c is 0 or 1.
• non-aromatic cyclic amines of Structure XVI include, but are not limited to morpholine, N-methylmorpholine, 2,6- dimethylmorpholine, 2,2,6,6-tetramethylmorpholine, N-hydroxyethyl morpholine, N- ethyl morpholine, thiomorpholine, N-methylthiomorpholine, 2,6- dimethylthiomorpholine, 2,2,6,6-tetramethylthiomorpholine, piperidine, N- hydroxyethylpiperidine, 2,6-dimethyl piperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, N-methylpyrrolidine, N-ethyl pyrrolidine, 2,5-dimethylpyrrolidine 2,2,5,5- tetramethylpyrrolidine, piperazine, N, N'-dimethylpiperazine, and N, N 1 - diethylpiperazine.
• Preferred non-aromatic cyclic amines of Structure XVI are those in which R 47 is a Ci-C ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl, or a C ⁇ -Cio substituted or unsubstituted aryl and where R 47 is a hydrogen atom, at least two of R 48 , R 49 , R 50 , and R 51 are independently a C 1 -C 6 substituted or unsubstituted linear, branched, or cyclic alkyl.
• non-aromatic cyclic amines include, but are not limited to, N-methylmorpholine, 2,6-dimethylmorpholine, 2,2,6,6- tetramethylmorpholine, N-hydroxyethyl morpholine, N-ethyl morpholine, N- hydroxyethylpiperidine, 2,6-dimethyi piperidine, 2,2,6,6-tetramethylpiperidine , N- methylpyrrolidine, N-ethyl pyrrolidine, 2, 5, -dimethyl pyrrolidine 2,2,5,5- tetramethylpyrrolidine, N, N'-dimethylpiperazine, and N, N'-diethylpiperazine.
• More preferred non-aromatic cyclic amines of Structure XVI are those in which R 47 is a CrC ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl, or a C ⁇ -Cio substituted or unsubstituted aryl and where R 47 is a hydrogen atom, R 48 , R 49 , R 50 , and R 51 are each independently a CrC ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl.
• non-aromatic cyclic amines include, but are not limited to, N-methylmorpholine, 2,2,6,6-tetramethylmorpholine, N-hydroxyethyl morpholine, N-ethyl morpholine, N-hydroxyethylpiperidine, 2,2,6,6- tetramethylpiperidine , N-methylpyrolidine, N-ethyl pyrrolidine, 2,2,5,5- tetramethylpyrrolidine, N, N'-dimethylpiperazine, and N, N'-diethylpiperazine.
• non-aromatic cyclic amines of Structure XVI are those in which R 47 is a C-I-C ⁇ substituted or unsubstituted linear, branched, or cyclic alkyl.
• Most preferred examples of non-aromatic cyclic amines of Structure XVI include, but are not limited to, N-methylmorpholine, N-hydroxyethyl morpholine, N-ethyl morpholine, N-hydroxyethylpiperidine, N-methylpyrrolidine, N-ethyl pyrrolidine, N, N'- dimethylpiperazine, and N, N'-diethylpiperazine.
• L is an oxygen atom, a sulfur atom, NR 67 or CR 69 R 70 ;
• R 67 is a hydrogen atom, a d-C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, a C ⁇ -C IO substituted or unsubstituted aryl, or together with R 68 forms a second bond between L and the C atom to which R 68 is attached;
• R 69 and R 70 are independently selected from a hydrogen atom, a C1-C 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C ⁇ -Cio substituted or unsubstituted aryl;
• R 57 -R 66 are independently selected from a hydrogen atom, a CrC 6 substituted or unsubstituted linear, branched, or cyclic alkyl, or a C ⁇ -C-io substituted or unsub
• Preferred non-aromatic cyclic amines of Structure XVII are include, but are not limited to, 1,5-diazabicyclo[4.3.0]non-5-ene, 1 ,8-diazabicyclo[5.4.0]undec-7-ene and the compound shown below.
• tertiary alicyclic amines include, but are not limited to the following compounds where R 72 is a CrC 6 substituted or unsubstituted linear, branched, or cyclic alkyl or a C 6 -Ci 0 substituted or unsubstituted aryl.
• the quaternary ammonium hydroxides are ammonium hydroxides in which each of the four groups has a carbon atom attached to the positively charged nitrogen.
• the groups may be substituted or unsubstituted.
• Suitable quaternary ammonium hydroxides are described by Structure XVIII, in which R 36 , R 37 , R 38 , and R 39 are independently substituted or unsubstituted linear, branched, or cyclic alkyl, substituted or unsubstituted linear, branched or cyclic hydroxyalkyl, or substituted or unsubstituted phenyl.
• Examples of quaternary ammonium hydroxides of Structure XVIII include, but are not limited to, the following compounds.
• R 43 is a hydrogen atom or a substituted or unsubstituted Ci- C 20 alkyl group and q is an integer of from 0 to 20. In a preferred embodiment, q is an integer of from 0 to 10. In a more preferred embodiment, q is an integer from 0 to 5. In a most preferred embodiment, q is an integer from 0 to 3.
• Preferred quaternary ammonium hydroxides are those of Structure XVIII in which R 36 , R 37 , R 38 , and R 39 are independently substituted or unsubstituted linear, branched, or cyclic alkyl, or substituted or unsubstituted linear, branched or cyclic hydroxyalkyl.
• More preferred quaternary ammonium hydroxides are those of Structure XVIII in which R 36 , R 37 , R 38 , and R 39 are independently C 1 -Ci 0 linear, branched, or cyclic substituted or unsubstituted alkyl, or C 2 -C 2 Q substituted or unsubstituted, linear, branched or cyclic hydroxyalkyl.
• Most preferred quaternary ammonium hydroxides are those of Structure XVIII in which R 36 , R 37 , R 38 , and R 39 are independently Ci-C 4 linear, branched, or cyclic substituted or unsubstituted alkyl, or C 2 -C 4 substituted or unsubstituted, linear or branched hydroxyalkyl.
• a mixture of at least two basic compounds having different structures selected from the basic compounds described above may be used as the basic compound of component (C).
• the basic compound of component (C) may be used as the basic compound of component (C).
• two basic compounds having different structures, three basic compounds having different structures or four or more basic compounds having different structures may be used.
• an amount of the basic compound that is used in the least amount is not less than 10% by weight based on the total amount of the basic compounds used.
• the shutter of a nonlaser based stepper is typically not designed to operate reproducibly at a very high photospeed (e.g., at a very low energy dose).
• a photosensitive composition with a very high photospeed typically yields inconsistent exposure results. Addition of a basic compound described above in such a composition can decrease its photospeed and therefore reproducibly controls the exposure results of such a composition.
• the photosensitive composition described in this disclosure can form 8 ⁇ m features at an exposure energy of at least about 125 mJ/cm 2 (e.g., at least about 175 mJ/cm 2 ) and/or at most about 500 mJ/cm 2 (e.g., at most about 200 mJ/cm 2 ) by using an i-line stepper.
• Other advantages of using a basic compound described above in a photosensitive include improving the shelf life of the composition, removing chemical undercut of a film made by these compositions (e.g., in the presence of an epoxy adhesion promoter), and reducing the thickness loss of an unexposed film made by the composition during a lithographic process.
• the inventors surprising discovered that certain basic compounds can increase the photospeed of a photosensitive compound (e.g., a PBO precursor) described in this disclosure.
• a photosensitive compound e.g., a PBO precursor
• examples of such basic compounds include tertiary amines of Structure XIV in which R 30 , R 31 , and R 32 are C 6 -C 30 substituted or unsubstituted aryl (e.g., phenyl).
• Such basic compounds can be used in a photosensitive composition if the composition has a very slow photospeed.
• such basic compounds can be used in combination with other basic compounds described above to adjust the photospeed of a photosensitive compound described in this disclosure to an optimal value.
• a chemically amplified positive working photosensitive polybenzoxazole precursor composition of the present disclosure can contain one or more polybenzoxazole precursors I, II, or II * at about 10 wt.% to about 50 wt.% of the composition.
• the PBO precursor polymer used in a chemically amplified positive working photosensitive polybenzoxazole precursor composition of the present disclosure may contain a mixture of R 1 groups, R 2 groups, or R 1 and EOR 2 groups.
• a mixture of polybenzoxazole precursor polymers may be employed which, between the polybenzoxazole precursor polymers, have different R 1 groups, EOR 2 groups, or the first polybenzoxazole precursor polymer having an R 1 group and the second polybenzoxazole precursor polymer having an EOR 2 group.
• Structure I may be replaced by other organic solvent soluble, aqueous base soluble, aromatic or heterocyclic group polymers or copolymers.
• organic solvent soluble, aqueous base soluble, aromatic or heterocyclic group polymers or copolymers may include polyimides, polyamic esters, polybenzoimidazoles, polybenzothiazoles, polytriazoles, polyquinazolones, polyquinazolindiones, polyquinacridones, polybenxazinones, polyanthrazolines, polyoxadiazoles, polyhydantoins, polyindophenazines, or polythiadiazoles.
• Polyamic acids may also be employed as a co-resin, but preferably is employed only when a high-energy activation acid sensitive group (e.g. a tertiary ester) is employed on the polybenzoxazole precursor I, Il or II * .
• the amount of PAG ranges from about 0.5 to about 20% (wt) based on amount of polybenzoxazole precursor.
• a preferred amount of PAG is from about 2 to about 15% (wt) based on the amount of polybenzoxazole precursor.
• a more preferred amount of PAG is from about 2 to about 10% (wt) based on the amount of polybenzoxazole precursor.
• the amount of optional sensitizer can be from about 0.1 to about 5 % (wt) based on the amount of polybenzoxazole precursor.
• the photoacid generator may be used alone or in combination with one or more photoacid generators. The percentage of each photoacid generator in photoacid generator mixtures is between about 10% to about 90% of the total photoacid generator mixture. Preferred photoacid generator mixtures contain about 2 or 3 photoacid generators. Such mixtures may be of the same class or different classes.
• the amount of basic compound ranges from about 0.001 wt% to about
• a preferred amount of basic compound is from about 0.01 wt% to about 1.5 wt % of the total photosensitive composition.
• a more preferred amount of basic compound is from about 0.02 wt% to about 1 wt % of the total photosensitive composition.
• the most preferred amount of basic compound is from about 0.03 wt% to about 0.5 wt % of the total photosensitive composition.
• a chemically amplified positive working photosensitive polybenzoxazole (PBO) precursor composition described in this disclosure can further include one or more solvents.
• the amount of solvent in the composition can be from about 40% (wt) to about 87% (wt).
• the preferred amount is from about 45% (wt) to about 70% (wt), more preferred amount is from about 47.5% (wt) to about 65% (wt), more preferred amount is from about 50% (wt) to about 60% (wt).
• the solvent should not interfere with the photoacid generation from PAG or with the acid- catalyzed de-blocking reaction, should dissolve all components and should cast a good film.
• Suitable solvents include, but are not limited to organic solvents, such as gamma- butyrolactone (GBL), propylene glycol methyl ether acetate (PGMEA), methoxy ethyl ether and mixtures thereof.
• the preferred solvents are propylene glycol methyl ether acetate (PGMEA) and gamma-butyrolactone.
• the most preferred solvent is propylene glycol methyl ether acetate (PGMEA) or a mixture of propylene glycol methyl ether acetate and gamma-butyrolactone.
• a chemically amplified positive working photosensitive PBO precursor compositions of the present disclosure can optionally include at least one plasticizer.
• the plasticizer should have a lower volatility than the solvent employed at the typical bake temperatures of about 100 0 C to about 150 0 C 1 so that it remains in the film after the softbake. This typically means that the plasticizer of this disclosure has a higher boiling point than the solvent employed, unless interaction of the functional groups of the plasticizer with other components of the chemically amplified positive working photosensitive PBO precursor composition decreases its volatility sufficiently. It is preferred that this boiling point differential is at least about 10 0 C. A more preferred boiling point differential is at least about 15°C.
• the amount of optional plasticizer used in a chemically amplified positive working photosensitive PBO precursor composition of this disclosure is from about 0.1 wt% to about 20 wt% of the total weight of the composition, preferably, from about 1 wt% to about 10 wt%, more preferably, from about 1.25 wt% to about 7.5 wt% and most preferably, from about 1.5 wt% to about 5 wt%.
• the plasticizers may be blended together in any suitable ratio.
• the optional plasticizer is at least one polyhydroxy compound with at least two OH groups and whose boiling point is higher than the boiling point of the chemically amplified positive working photosensitive PBO precursor composition solvent.
• polyhydroxy compounds with at least two OH groups are, but are not limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, tripropylene glycol, polypropylene glycol, glycerol, butane diol, hexane diol, sorbitol, cyclohexanediol, 4,8-bis(hydroxyrnethyl)-tricyclo(5.2.1.0/2,6)decane and a 2- oxepanone co-polymer with 2-ethyl-2-(hydroxymethyl)-1 ,3-propanediol.
• Preferred polyhydroxy compound with at least two OH groups are diethylene glycol, tripropylene glycol, and a 2-oxepanone co-polymer with 2-ethyl-2-(hydroxymethyl)- 1 ,3-propanediol. More preferred polyhydroxy compound with at least two OH groups are tripropylene glycol and a 2-oxepanone co-polymer with 2-ethyl-2- (hydroxymethyl)-1 ,3-propanediol.
• the optional plasticizer is at least one saturated glycol mono ether whose boiling point is higher than the boiling point of the chemically amplified positive working photosensitive PBO precursor composition solvent.
• saturated glycol mono ethers include, but are not limited to, saturated mono ethers of tripropylene glycol, tetrapropylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.
• Preferred saturated glycol mono ethers are saturated mono ethers of tripropylene glycol, triethylene glycol and tetraethylene glycol. More preferred saturated glycol mono ethers are tri(propylene glycol)methyl ether, tri(propylene glycol)propyl ether and tri(propylene glycol)butyl ether.
• the optional plasticizer is at least one carboxylic acid ester whose boiling point is higher than the boiling point of the chemically amplified positive working photosensitive PBO precursor composition solvent.
• Examples include, but are not limited to, ethyl cyclohexyl acetate, propyl benzoate, butyl benzoate, n-butyl cinnamate, ethyI-3,3'- diethoxypropionate, dimethyl succinate, diisopropyl succinate, dimethyl maleate, dimethyl malonate, diethyl adipate, diethyl acetamidomalonate, diethyl allylmalonate, and dimethyl cyclohexane-1 ,4-dicarboxylate, mixture of cis and trans isomers.
• the carboxylic acid ester is derived from a carboxylic acid containing at least two carboxylic acid groups.
• Examples include, but are not limited to, dimethyl succinate, .diisopropyl succinate, dimethyl maleate, dimethyl malonate, diethyl adipate, diethyl acetamidomalonate, diethyl allylmalonate, and dimethyl cyclohexane-1 ,4-dicarboxylate, including mixtures of cis and trans isomers thereof.
• Preferred embodiments of the present disclosures are chemically amplified positive working photosensitive PBO precursor compositions including at least one plasticizer selected from the group consisting of polyhydroxy compounds with at least two OH groups and glycol ethers.
• More preferred embodiments of the present disclosures are chemically amplified positive working photosensitive PBO precursor compositions including at least one plasticizer selected from the group consisting of polyhydroxy compounds with at least two OH groups.
• a positive chemically amplified resist formulation of the present disclosure can also contain other additives, such as, but not limited to, surfactants, dyes, profile enhancing additives, adhesion promoters, etc.
• the amount of adhesion promoter may range from about
• a preferred amount of adhesion promoter is from about 0.5 wt. % to about 5 wt. % based on the amount of polybenzoxazole precursor polymer.
• a more preferred amount of adhesion promoter is from about 1 wt. % to about 4 wt. % based on the amount of polybenzoxazole precursor polymer.
• Suitable adhesion promoters include, for example, alkoxysilanes, and mixtures or derivatives thereof.
• each R 21 is independently a Ci-C 4 alkyl group or a C 5 -C 7 cycloalkyl group and each R 22 is independently a Ci-C 4 alkyl group, a Ci-C 4 alkoxy group, a C 5 -C 7 cycloalkyl group or a C 5 -C 7 cycloalkoxy group;
• d is an integer from 0 to 3 and n is an integer from 1 to about 6.
• R 23 is one of the following moieties:
• each R and R J25 are independently a substituted or unsubstituted C 1 -C 4 alkyl group or a C 5 -C 7 cycloalkyl group, and R 26 is a C 1 -C 4 alkyl group and a C 5 -C cycloalkyl group.
• Preferred adhesion promoters are those in which R 23 is selected from the group consisting of
• adhesion promoters include, but are not limited to the following compounds.
• the present disclosure includes a process for forming a relief pattern.
• the process includes the steps of: (a) providing a substrate, (b) coating on said substrate, a positive-working photosensitive composition including at least one polybenzoxazole precursor polymer having Structure I or Il or II*; at least one photoacid generator which releases acid upon irradiation; at least one basic compound; and at least one solvent (all as described above), thereby forming a coated substrate; (c) exposing the coated substrate to actinic radiation; (d) post exposure baking the coated substrate at an elevated temperature of about 7O 0 C to about 15O 0 C; (e) developing the coated substrate with an aqueous base developer, thereby forming a developed relief pattern; and (f) baking the substrate at an elevated temperature sufficient to cure the composition to produce a polybenzoxazole relief image.
• the curing temperature can range from about 25O 0 C to about 400 0 C.
• R 30 , R 31 , and R 32 are independently selected from the group consisting of a C 1 -C 30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C 3 -C 30 tertiary aminoalkyl, a C 2 -C 30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, and a CrC 30 alkyl group containing at least one ether linkage, provided that the number of carbon atoms in the tertiary amine of Structure XIV is at least 6, may be employed.
• the positive working photosensitive PBO precursor composition of this disclosure is coated on a suitable substrate.
• the coating can have a thickness of at least about 4 ⁇ m. In a preferred embodiment the coating thickness is at least 6 ⁇ m. In a more preferred embodiment the coating thickness is at least 8 ⁇ m.
• the substrate may be, for example, semiconductor materials such as a silicon wafer, compound semiconductor (Groups Ill-V) or (Groups II-VI) wafer, a ceramic, glass or quartz substrate.
• the substrates may also contain films or structures used for electronic circuit fabrication such as organic or inorganic dielectrics, copper or other wiring metals.
• the substrate may be optionally treated before coating with an adhesion promoter or adhesion promoter composition before the first coating step or the photosensitive composition may employ an internal adhesion promoter.
• Any suitable method of treatment of the substrate with adhesion promoter known to those skilled in the art may be employed. Examples include treatment of the substrate with adhesion promoter vapors, solutions or at 100% concentration. The time and temperature of treatment will depend on the particular substrate, adhesion promoter, and method, which may employ elevated temperatures. Any suitable adhesion promoter may be employed.
• Classes of suitable adhesion promoters include, but are not limited to, vinylalkoxysilanes, methacryloxalkoxysilanes, mercaptoalkoxysilanes, epoxyalkoxysilanes and glycidoxyalkoxysilanes.
• adhesion promoters include, but are not limited to, gamma- glycidoxypropylmethyldimethoxysilane, gam/na-glycidoxypropyl- methyldiethoxysilane, gra/nma-mercaptopropylmethyldimethoxysilane, 3-methacryl- oxypropyldimethoxymethylsilane, and 3-methacryloxypropyltrimethoxysilane.
• gamma-glycidoxypropylmethyldimethoxysilane is more preferred. Additional suitable adhesion promoters are described in "Silane Coupling Agent" Edwin P. Plueddemann, 1982 Plenum Press, New York, which is incorporated herein by reference.
• Coating methods include, but are not limited to, spray coating, spin coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and immersion coating.
• the resulting film is prebaked at an elevated temperature.
• the bake may be carried out at one or more temperatures within the temperature range of about 70 0 C to about 15O 0 C.
• the temperature range is about 8O 0 C to about 13O 0 C, more preferably the temperature range is about 9O 0 C to about 12O 0 C and most preferably the coatings are baked from about 100 0 C to about 120 0 C.
• the duration of the bake is for several minutes to half an hour, depending on the method used to evaporate the remaining solvent.
• Any suitable baking means may be employed. Examples of suitable baking means include, but are not limited to, hot plates and convection ovens.
• the resulting dry film has a thickness of from about 3 to about 50 microns or more preferably from about 4 to about 20 microns or most preferably from about 5 to about 15 microns.
• the resulting dry film is exposed to actinic rays in a preferred pattern through a mask.
• actinic rays X-rays, electron beam, ultraviolet rays, visible light, and the like can be used as actinic rays.
• the most preferred rays are those with wavelength of 436 nm (g-line) and 365 nm (i-line).
• the exposed and chemically amplified positive working photosensitive PBO precursor composition coated substrate may be advantageous to heat the exposed and chemically amplified positive working photosensitive PBO precursor composition coated substrate to a temperature between about 7O 0 C to about 15O 0 C.
• the temperature range is about 8O 0 C to about 14O 0 C. More preferably the temperature range is about 9O 0 C to about 13O 0 C. Most preferably the temperature range is about 100 0 C to about 13O 0 C.
• the exposed and coated substrate is heated in this temperature range for a short period of time, typically several seconds to several minutes and may be carried out using any suitable heating means.
• Preferred means include baking on a hot plate or in a convection oven. This process step is commonly referred to in the art as post-exposure baking
• the aqueous developer contains a water soluble base.
• suitable bases include, but are not limited to, inorganic alkalis (e.g., potassium hydroxide, sodium hydroxide, ammonia water), primary amines (e.g., ethylamine, n- propylamine), secondary amines (e.g. diethylamine, di-n-propylamine), tertiary amines (e.g., triethylamine), alcoholamines (e.g.
• inorganic alkalis e.g., potassium hydroxide, sodium hydroxide, ammonia water
• primary amines e.g., ethylamine, n- propylamine
• secondary amines e.g. diethylamine, di-n-propylamine
• tertiary amines e.g., triethylamine
• alcoholamines e.g.
• quaternary ammonium salts e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide
• concentration of base employed will vary depending on the base solubility of the polymer employed and the specific base employed.
• the most preferred developers are those containing tetramethylammonium hydroxide (TMAH). Suitable concentrations of TMAH range from about 1 % to about 5%.
• TMAH tetramethylammonium hydroxide
• TMAH tetramethylammonium hydroxide
• a surfactant can be added to the developer.
• Development can be carried out by means of immersion, spray, puddle, or other similar developing methods at temperatures from about 10 0 C to about 4O 0 C for about 30 seconds to about 5 minutes.
• the relief pattern may be optionally rinsed using deionized water and dried by spinning, baking on a hot plate, in an oven, or other suitable means.
• the exposed, coated and developed substrate may be advantageous to heat the exposed, coated and developed substrate to a temperature between about 7O 0 C to about 22O 0 C.
• the temperature range is about 8O 0 C to about 21O 0 C. More preferably the temperature range is about 8O 0 C to about 200 0 C.
• the most preferred temperature range is about 90 0 C to about 18O 0 C.
• Preferred means include baking on a hot plate or in a convection oven. This process step is commonly referred to in the art as post- develop baking.
• the benzoxazole ring is then formed by curing of the uncured relief pattern to obtain the final high heat resistant pattern. Curing is performed by baking the developed, uncured relief pattern at or above the glass transition temperature T 9 of the positive working photosensitive PBO precursor composition to obtain the benzoxazole ring that provides high heat resistance. Typically, temperatures above about 200 0 C are used. Preferably, temperatures from about 25O 0 C to about 400 0 C
• the curing time is from about 15 minutes to about 24 hours depending on the particular heating method employed. A more preferred range for the curing time is from about 20 minutes to about 5 hours and the most preferred range of curing time is from about 30 minutes to about 3 hours.
• Curing can be done in air or preferably, under a blanket of nitrogen and may be carried by any suitable heating means. Preferred means include baking on a hot plate, a convection oven, tube furnace, vertical tube furnace, or rapid thermal processor. Alternatively, curing may be effected by the action of microwave or infrared radiation.
• Example 1 (200 g) was dissolved in a mixture of 600 g of diglyme and 300 g of propylene glycol methyl ether acetate (PGMEA). Residual water was removed as an azeotrope with PGMEA and diglyme using a rotary evaporator at 65 0 C (10-12 torr). About 550 g of solvent was removed during the azeotropic distillation. The reaction solution was placed under a N 2 blanket and equipped with a magnetic stirrer. Nadic anhydride (7 g) was added to the solution and followed by the addition of 10 g of pyridine. The reaction was stirred overnight at 5O 0 C.
• PGMEA propylene glycol methyl ether acetate
• reaction mixture was diluted with 500 g of tetrahydrofuran (THF) and precipitated into 8 liters of a 50:50 methanol: water mixture.
• THF tetrahydrofuran
• the polymer was collected by filtration and vacuum dried at 8O 0 C.
• H 3 C B H or CH 3
• the organic phase was separated from the aqueous phase.
• To the organic phase was added 78.6 g of acetone and 63.0 g of deionized water and the mixture was shaken for a few minutes.
• the organic phase was again separated from the aqueous phase. This process was repeated two more times each with 78.6 g of acetone and 63.0 g of deionized water.
• the resulting solution was then concentrated to 50% solids by using a rotary evaporator at 65 0 C (10-12 torr).
• a positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 125°C, resulting in a film thickness of 9.04 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 130 0 C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution using two 30 second puddle development steps with spin steps to remove spent developer in between applications of developer.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern. No unexposed film thickness loss was observed. 2 ⁇ m and 8 ⁇ m features were resolved at exposure energies of 200 m J/cm 2 and 175 mJ/cm 2 respectively.
• Example 2 [0144] In Examples 2 - 4 and Comparative Example 1 , all the formulations were exactly as that of Example 1 except the amount of 1 ,8-diazabicyclo[5.4.0] undec-7-ene (DBU) was different. The formulations were tested lithographically employing the process described in Example 1. The amount of DBU in the formulation and the exposure required to clear 2 and 8 ⁇ m via pads are summarized in Table 1.
• DBU 1 ,8-diazabicyclo[5.4.0] undec-7-ene
• a positive acting photosensitive composition was prepared by mixing
• Example 6 [0149] In Examples 6 - 9 and Comparative Example 2 all the formulations were exactly as the formulation of Example 5 except the amount of 1 ,8- diazabicyclo[5.4.0] undec-7-ene (DBU) was different. The formulations were tested lithographically using the procedure described in Example 1. The amount of DBU and the exposure required to open 8 ⁇ m vias are listed in Table 2. Addition of a base surprisingly helped to decrease unexposed film thickness loss.
• DBU diazabicyclo[5.4.0] undec-7-ene
• Example 10 - 15 all the formulations were exactly the same as the formulation of Example 1 except the identity of the basic compound and the concentration of it were varied.
• the lithographic process for Examples 10-15 was the same as Example 1.
• the basic compound, its concentration, and the exposure required to clear a 8 ⁇ m via pad are summarized in Table 3.
• the molar amount of basic compound in Examples 11 - 15 is equal to that of Example 10.
• Example 16-18 all the formulations were exactly the same as the formulation of Example 1 except the identity of the basic compound and the concentration of it were varied.
• the lithographic process for Examples 16-18 was the same as Example 1.
• the basic compound, its concentration, and the exposure required to clear a 8 ⁇ m via pad are summarized in Table 4.
• a positive acting photosensitive composition was prepared by mixing
• composition of Example 19 was surprisingly stable relatively to compositions without the basic compound for photospeed.
• Example 19 A composition similar to Example 19 was prepared except no DBU was used. The results of lithographic evaluation are shown in Table 6.
• a positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 2 minutes at 120 0 C, resulting in a film thickness of 8.97 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 120 0 C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution in a 60 second puddle development steps.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• Unexposed film thickness loss was 5.28%. 8 ⁇ m features were resolved at an exposure energy of 100 mJ/cm 2 .
• NIT N-hydroxynaphthalimide trifluoromethanesulfonate
• a higher base concentration will be necessary to slow the photospeed of compositions containing PAGs which generate strong acids such as perfluoromethanesulfonic acids after exposure.
• the yield was almost quantitative and the inherent viscosity (iv) of the polymer was 0.179 dl/g measured in NMP at a concentration of 0.5 g/dl at 25 0 C.
• a positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 80 0 C, resulting in a film thickness of 8.56 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 100 0 C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution using two 60 second puddle development steps with spin steps to remove spent developer in between applications of developer.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• the film thickness after development was 8.30 ⁇ m. Unexposed film thickness loss was 3.06%. 8 ⁇ m features were resolved at exposure energy of 350 mJ/cm 2 . These features were carefully investigated by SEM and no chemical undercut was observed.
• Comparative Example 4 The same positive acting photosensitive composition was prepared as in Example 21 except no 1 ,8-diazabicyclo[5.4.0] undec-7-ene (DBU) was used.
• DBU ,8-diazabicyclo[5.4.0] undec-7-ene
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 80 0 C, resulting in a film thickness of 8.40 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 1OQ 0 C for 90 seconds.
• the wafer was developed with a fresh 2.38% aqueous TMAH solution using two standing 60 second puddle development steps with spin steps to remove spent developer in between applications of developer.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• the film thickness after development was 8.06 ⁇ m. Unexposed film thickness loss was 3.42%. 8 ⁇ m features were resolved at exposure energy of 300 mj/cm 2 . These features were carefully investigated by SEM and some chemical undercut
• Example 21 and Comparative Example 4 unexpectedly and surprisingly showed that presence of a base can remove chemical undercut of a film made by this composition.
• a positive acting photosensitive composition was prepared by mixing 200 parts by weight of a polymer solution prepared by the method described in Synthesis Example 4, 2 parts by weight of 2-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, , 0.2 parts by weight of 1 ,4- dimethylpiperazine, 6 parts by weight of (5-propylsulfonyloxyimino-5H-thiophen-2- ylidene)-2-methylphenyl-acetonitrile, 6 parts by weight of propylene carbonate, 4 parts by weight of 4,4'-sulfonyl diphenol, and 57.9 parts by weight GBL and filtered through a 0.2 ⁇ m Teflon filter.
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 115°C, resulting in a film thickness of 8.54 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 135°C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution using one standing 60 second puddle development step.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• the film thickness after development was 8.38 ⁇ m. Unexposed film thickness loss was 1.84%. 8 ⁇ m features were resolved at an exposure energy of 520 mj/cm 2 .
• Examples 23 - 27 and Comparative Examples 5 and 6 all the formulations were exactly the same as the formulation of Example 21 except the identity of the basic compound and the concentration of it were varied.
• the lithographical process for Examples 23 - 27 and Comparative Examples 5 and 6 were the same as Example 22.
• the basic compound, its concentration, and the exposure required to clear a 8 ⁇ m via pad are summarized in Table 7.
• the molar amount of basic compound in Examples 23 - 27 and Comparative Example 5 is equal to that of Example 22.
• the PBO precursor polymer obtained in Synthesis Example 1 (100 g) was dissolved in a mixture of 500 g of diglyme and 300 g of propylene glycol methyl ether acetate (PGMEA). Residual water was removed as an azeotrope with PGMEA and diglyme using vacuum distillation at 65 0 C (10-12 torr). About 400 g of solvents was removed during the azeotropic distillation. The reaction solution was placed under a N 2 blanket. The reaction mixture was cooled on an ice bath down to 5 0 C and 3.2 g of pyridine was added at once followed by 8.5 g of p-toluene sulfonic acid chloride. The reaction mixture was allowed to warmed up to room temperature and stirred overnight.
• PGMEA propylene glycol methyl ether acetate
• the reaction mixture was precipitated into 6 liters of water while stirring.
• the precipitated polymer was collected by filtration and air dried overnight.
• the polymer was dissolved in 500-600 g of acetone and precipitated into 6 liters of a water/methanol (70/30) mixture.
• the polymer was again collected by filtration and air-dried for several hours.
• the still damp polymer cake was dissolved in a mixture of 70Og of THF and 70 ml of water.
• An ion exchange resin UP604 (4Og) available from Rohm and Haas, was added and the solution was rolled for 1 hour.
• the final product was precipitated in 7 liters of water, filtered, air-dried overnight followed by 24 hour drying in vacuum oven at 9O 0 C.
• a polymer prepared with the procedure from Synthesis Example 9 (30 g) is dissolved in 15O g of diglyme. Residual water is removed as an azeotrope with diglyme using vacuum distillation at 65 0 C (10 - 12 torr). About 50 g of solvents is removed during the azeotrope distillation. Water content in reaction mixture ranges from 60-150 ppm.
• the reaction solution is placed under a N 2 blanket and equipped with a magnetic stirrer and cooled down to 25 0 C.
• Ethyl vinyl ether (4 ml) is added via syringe, followed by 1 ml of a 1.5 wt% solution of p-toluene sulfonic acid in PGMEA. The reaction mixture is stirred for 2 hours at 25 0 C and triethyl amine (0.3 ml) is added.
• the reaction mixture is precipitated into 2 liters of a water/methanol mixture (50/50) mixture.
• the polymer is separated by filtration, air dried for 2 hours and dissolved in 200 ml of THF.
• the polymer is precipitated two more times into 2 liters of a water/methanol mixture (50/50), filtered and air-dried. Then the polymer is vacuum-dried at 45 0 C overnight.
• PBO precursor polymer is blocked with ethyl vinyl ether. This can be determined by integration of the acetal peak at 5.6 ppm and the phenol peak at 10.4 ppm.
• a positive acting photosensitive composition is prepared by mixing 100 parts by weight of a polymer prepared by the method described in Synthesis Example 10, 4 parts by weight of (3-glycidoxypropyl)methyldimethoxysilane, 0.5 parts by weight of a 25% solution of tetraethylammonium hydroxide in methanol, 4 parts by weight of photoacid generator shown below, 15 parts of di(propylene)glycol, 8 parts by weight of 2,2-bis(4-hydroxyphenyl)propane, and 15 parts by weight ethyl lactate and 100 parts by weight GBL and is filtered through a 0.2 ⁇ m Teflon filter.
• a silicon wafer is then coated with the photosensitive composition from above and hotplate baked for 2 minutes at 110°C, resulting in a film thickness of 8.50 ⁇ m.
• the film is exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer are exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer is post exposure baked at 13O 0 C for 60 seconds.
• the wafer is developed with 2.38% aqueous TMAH solution using one 45 second puddle development step.
• the developed film is rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern. 8 ⁇ m features are resolved.
• a polymer prepared in the same way as in Synthesis Example 6 (100 g) is dissolved in 1 ,000 g of diglyme. Residual water is removed as an azeotrope with diglyme using a rotary evaporator at 65 0 C (10 - 12 torr). About 500 g of the solvent is removed during the azeotrope distillation. The reaction solution is placed under a N 2 blanket and equipped with a magnetic stirrer, f-butyl bromoacetate, (21.2 g, 107 mmol) is added, followed by 9.3 g, 117.6 mmol of pyridine. The reaction mixture is stirred for 5 hours at 4O 0 C.
• the resulting mixture is added dropwise to 10 liters of water, yielding a white precipitate.
• the precipitate is washed 5 times with water, filtered, and dried in vacuum below 4O 0 C to give 101 g of t- butoxycarbonylmethyloxy-bearing polymer.
• the product is analyzed by proton-NMR. From a peak of phenyl at 6 to 7 ppm and peaks of f-butyl and methylene at 1 to 2 ppm, the f-butoxycarbonylmethyloxy introduction rate is calculated to be approximately 30 mole% of available OH groups.
• a positive acting photosensitive composition is prepared by mixing 100 parts by weight of a polymer prepared by the method described in Synthesis Example 11 , 2.5 parts by weight of 3-cyanoypropyltrimethoxysilane, 0.2 parts by weight of N-tert-butyl isopropylamine, 3 parts by weight of photoacid generator shown below, 7.5 parts of dimethyl succinate, 6 parts by weight of Bisphenol F, 25 parts by weight ethyl lactate, 25 parts by weight of PGME ⁇ A and 65 parts by weight GBL and is filtered through a 0.2 ⁇ m Teflon filter.
• a silicon wafer is then coated with the photosensitive composition from above and hotplate baked for 150 seconds at 95°C, resulting in a film thickness of 8.50 ⁇ m.
• the film is exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer are exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer is post exposure baked at 132.5°C for 50 seconds.
• the wafer is developed with 2.38% aqueous TMAH solution using one 55 second puddle development step.
• the developed film is rinsed with deionized water and dried by spinning for 12 seconds at 4500 rpm to provide a relief pattern. 8 ⁇ m features are resolved.
• This polymer is prepared according to Synthesis Example 2 except the starting polymer is the one prepared by Synthesis Example 12.
• a positive acting photosensitive composition is prepared by mixing 80 parts by weight of a polymer prepared by the method described in Synthesis Example 14, 120 parts by weight of a polymer prepared by the method described in Synthesis Example 4, 4 part by weight of (3-glycidoxypropyl)methyldiethoxysilane, 0.1 parts by weight of N-tert-butyl isopropylamine, 0.1 parts by weight of dicyclohexylamine, 6.5 parts by weight of photoacid generator shown below, 8 parts of 2-oxepanone co-polymer with 2-ethyl-2-(hydroxymethyl)-1 ,3-propanediol, 10 parts by weight of 3,3-Bis(4-hydroxyphenyl)-1 ,3-dihydroindol-2-one, 8 parts by weight ethyl lactate, 8 parts by weight of PGMEA and 8 parts by weight GBL and is filtered through a 0.2 ⁇ m Teflon filter.
• a silicon wafer is then coated with the photosensitive composition from above and hotplate baked for 210 seconds at 100 0 C, resulting in a film thickness of 8.70 ⁇ m.
• the film is exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer are exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer is post exposure baked at 135 0 C for 75 seconds.
• the wafer is developed with 2.38% aqueous TMAH solution using one 75 second puddle development step.
• the developed film is rinsed with deionized water and dried by spinning for 15 seconds at 4800 rpm to provide a relief pattern. 8 ⁇ m features are resolved.
• This polymer is prepared according to Synthesis Example 2 except the starting polymer is the one prepared by Synthesis Example 15.
• This polymer is prepared according to Synthesis Example 4 except the starting polymer is the one prepared by Synthesis Example 16.
• a positive acting photosensitive composition is prepared by mixing 150 parts by weight of a polymer prepared by the method described in Synthesis
• Example 17 50 parts by weight of a polymer prepared by the method described in Synthesis Example 14, 4 part by weight of S-(octanoyl)mercaptopropyltriethoxy- silane, 0.1 parts by weight of N-methylpyrolidine, 0.1 parts by weight of N, N'- diethylpiperazine, 2 parts by weight of photoacid generator shown below, 2 parts by weight of (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-2-methylphenyl- acetonitrile, 12 parts of tri(propylene glycol)butyl ether, 6 parts by weight of 3,4- dihydroxy benzophenone, 8 parts by weight N,N-dimethylformamide (DMF), and 10 parts by weight of propylene glycol methyl ether (PGME) and is filtered through a 0.2 ⁇ m Teflon filter.
• a silicon wafer is then coated with the photosensitive composition from above and hotplate baked for 4 minutes at 11O 0 C 1 resulting in a film thickness of 9.0 ⁇ m.
• the film is exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer are exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer is post exposure baked at 13O 0 C for 120 seconds.
• the wafer is developed with 2.38% aqueous TMAH solution using two 40 second puddle development step.
• the developed film is rinsed with deionized water and dried by spinning for 20 seconds at 4900 rpm to provide a relief pattern. 8 ⁇ m features are resolved.
• a positive acting photosensitive composition is prepared by mixing 50 parts by weight of a polymer prepared by the method described in Synthesis Example 17, 50 parts by weight of a polymer prepared by the method described in Synthesis Example 14, 100 parts by weight of a polymer prepared by the method described in Synthesis Example 4, 3.75 part by weight of (3-triethoxysilylpropyl)-f- butylcarbamate, 0.12 parts by weight of a tertiary base shown below, 3.5 parts by weight of tris(-f-butylphenyl)sulfonium benzenesulfonate, 1 parts by weight of 9,10- dibutoxyanthracene, 8 parts of di(propylene glycol) methyl ether, 7 parts by weight of di(propylene glycol) dimethyl ether), and 15 parts by weight of propylene glycol methyl ether (PGME) and is filtered through a 0.2 ⁇ m Teflon filter.
• PGME propylene glycol methyl ether
• a silicon wafer is then coated with the photosensitive composition from above and hotplate baked for 3.5 minutes at 112.5°C, resulting in a film thickness of 9.0 ⁇ m.
• the film is exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer are exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer is post exposure baked at 127.5°C for 95 seconds.
• the wafer is developed with 2.38% aqueous TMAH solution using two 45 second puddle development step.
• the developed film is rinsed with deionized water and dried by spinning for 20 seconds at 4900 rpm to provide a relief pattern. 8 ⁇ m features are resolved.
• a positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 115°C, resulting in a film thickness of 8.50 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 135 0 C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution using one standing 60 second puddle development step.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• the film thickness after development was 8.42 ⁇ m. Unexposed film thickness loss was 0.8%. 8 ⁇ m features were resolved at an exposure energy of 155 m J/cm 2 . These features were carefully investigated by SEM and some chemical undercut was observed.
• a positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 115°C, resulting in a film thickness of 8.54 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 135 0 C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution using one standing 60 second puddle development step.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• the film thickness after development was 8.46 ⁇ m. Unexposed film thickness loss was 0.99%. 8 ⁇ m features were resolved at an exposure energy of 105 mJ/cm 2 . These features were carefully investigated by SEM and some chemical undercut was observed. Comparative Example 9
• a positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 115°C, resulting in a film thickness of 8.54 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 135°C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution using one standing 60 second puddle development step.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• the film thickness after development was 8.46 ⁇ m. Unexposed film thickness loss was 0.99%. 8 ⁇ m features were resolved at an exposure energy of 100 mJ/cm 2 . These features were carefully investigated by SEM and some chemical undercut was observed.
• Example 33 A positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 115 0 C, resulting in a film thickness of 8.55 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 135°C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution using one standing 60 second puddle development step.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• the film thickness after development was 8.46 ⁇ m.
• Unexposed film thickness loss was 1.04%. 8 ⁇ m features were resolved at an exposure energy of 235 mJ/cm 2 . These features were carefully investigated by SEM and no chemical undercut was observed.
• Example 34 A positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 115°C, resulting in a film thickness of 8.64 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 135 0 C for 90 seconds.
• the wafer was developed with 2.38% aqueous TMAH solution using one standing 60 second puddle development step.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5000 rpm to provide a relief pattern.
• the film thickness after development was 8.49 ⁇ m. Unexposed film thickness loss was 1.70%. 8 ⁇ m features were resolved at an exposure energy of 335 mJ/cm 2 . These features were carefully investigated by SEM and no chemical undercut was observed.
• Example 35 A positive acting photosensitive composition was prepared by mixing
• a silicon wafer was then coated with the photosensitive composition from above and hotplate baked for 3 minutes at 115°C, resulting in a film thickness of 8.49 ⁇ m.
• the film was exposed utilizing an i-line stepper with a patterned exposure array. Segments of the film on the wafer were exposed at various levels of exposure energy using a Canon 4000 IE i-line stepper.
• the wafer was post exposure baked at 135°C for 90 seconds.
• the wafer was developed with a 2.38% aqueous TMAH solution using one standing 60 second puddle development step.
• the developed film was rinsed with deionized water and dried by spinning for 10 seconds at 5,000 rpm to provide a relief pattern.
• the film thickness after development was 8.40 ⁇ m. Unexposed film thickness loss was 1.02%. 8 ⁇ m features were resolved at an exposure energy of 200 mJ/cm 2 . These features were carefully investigated by SEM and no chemical undercut was observed.

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