Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3218—Carbocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds

Definitions

• the present invention relates to polycyclic polymers and particularly to photodefinable polymer compositions that include polycyclic polymers. Description of Related Art
• conducting lines must be made thinner and placed in closer proximity to one another.
• the reduction in spacing between conducting lines in the circuitry and packaging of such circuitry results in a concomitant increase in the efficiency and speed of the circuit enabling greater storage capacity, faster processing of information, and lower energy requirements.
• the reduction in spacing between conducting lines can cause an 0 increase in capacitive coupling of the lines resulting in greater crosstalk, higher capacitive losses, and an increased RC time constant.
• U.S. Patent No. 6,121,340 discloses a negative-working photodefinable dielectric composition comprising a photoinitiator and a polycyclic addition polymer comprising repeating units with pendant hydrolyzable functionalities (e.g., silyl ethers).
• the 5 photoinitiator Upon exposure to a radiation source, the 5 photoinitiator catalyzes the hydrolysis of the hydrolyzable groups to effect selective crosslinking in the polymer backbone to form a pattern.
• the dielectric material of the '340 patent is in and of itself photodefinable.
• the dielectric compositions disclosed in the '340 patent disadvantageously require the presence of moisture for the hydrolysis reaction to proceed. As known, the presence of such moisture in the dielectric layer can lead
• R 1 , R 2 , R 3 , and R 4 is independently selected from one of the following groups: (a) H, Ci to C 2 linear, branched, and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, and alkynyl; g Q (b) Ci to C 25 linear, branched, and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, and alkynyl containing one or more hetero atoms selected from O, N, and Si; (c) an epoxy containing group of structural formula II: -A O-CR 23 R 24 - (H) where A is a linking group selected from Ci to C 6 linear, branched, and cyclic alkylene, and R 23 and R 24 are independently selected from H, methyl, and
• R 23 and R 24 are as defined above, and each occurrence of R 21 and R 22 are independently selected from H, methyl and ethyl;
• R 1 , R 2 , R 3 , and R 4 linked together by a linking group selected from Ci to C 5 linear, branched, and cyclic alkylene and alkylene aryl; wherein n is an integer of from 1 to 25, R 5 is an acid labile group, R 6 is selected from H, Ci to C 6 linear, branched, and cyclic alkyl, an epoxy cont-iining group of structural formula LI as defined above; and where a portion of the repeat units having structural formula I contain at least one epoxy functional pendant group.
• a linking group selected from Ci to C 5 linear, branched, and cyclic alkylene and alkylene aryl
• n is an integer of from 1 to 25
• R 5 is an acid labile group
• R 6 is selected from H, Ci to C 6 linear, branched, and cyclic alkyl, an epoxy cont-iining group of structural formula LI as defined above; and where a portion of the repeat units having structural formula I contain at least one epoxy functional pendant group.
• photodefinable dielectric compositions that include polymer compositions as described above and a material that photonically forms a catalyst.
• FIG. 1 For exemplary embodiments of the present invention, are directed to methods of forming a photodefinable layer on a substrate and include providing the substrate, coating at least one side of the substrate with a composition that includes the copolymer composition and the material that photonically forms a catalyst described above, exposing the layer on the coated substrate to radiation, and curing the radiation-exposed layer.
• Additional examples in accordance with the present invention are directed to electrical or electronic devices cont-tining a layer that includes or is derived from the photodefinable dielectric compositions described above, as well as devices made using methods in accordance with the present invention.
• polymer composition is meant to include a synthesized copolymer, as well as residues from initiators, catalysts, and other elements attendant to the synthesis of the copolymer, where such residues are understood as not being co ' valently incorporated thereto.
• residues and other elements considered as part of the 1 O polymer composition are typically mixed or co-mingled with the copolymer such that they tend to remain with the copolymer when it is transferred between vessels or between solvent or dispersion media.
• Polymer composition also includes materials added after synthesis of the copolymer to provide specific properties to the polymer composition.
• low K composition refers in general to a material
• 1 5 having a low dielectric constant, typically a material with a dielectric constant less than that of thermally formed silicon dioxide and in particular to materials with a dielectric constant of less than about 3.9.
• Modulus is understood to mean the ratio of stress . to strain and unless otherwise indicated refers to the Young's Modulus or Tensile Modulus O measured in the linear elastic region of the stress-strain curve. Modulus values are measured in accordance with ASTM method D 1708-95.
• acid labile and “acid labile group” refer to a portion of a molecule, i.e. a group, that will react in the presence of acid in a catalytic manner.
• the term "photodefinable dielectric composition” refers to a composition capable of forming, in and of itself, a patterned layer on a substrate. That is to say a layer that does not require the use of another material layer formed thereover, for example a photoresist layer, to form the patterned layer.
• a photodefinable dielectric composition is understood as being useable as a permanent insulative material
• the photodefinable composition can form layers that can be employed in a pattern forming scheme with a variety of types of electromagnetic radiation, including but not limited to, ultra-violet (UV) radiation, deep ultraviolet (DUV) radiation, an electron beam, or X-ray radiation.
• UV ultra-violet
• DUV deep ultraviolet
• X-ray radiation X-ray radiation
• a material that photonically forms a catalyst refers to materials that, when exposed to an appropriate form of energy, non-limiting 5 examples being UV radiation, DUV radiation, an electron beam, and X-ray radiation, will break down, decompose, or in some other way alter their molecular composition to form a compound capable of catalyzing a crosslinking reaction in the photodefinable dielectric composition.
• the term “cure” is intended to refer to 1 0 crosshnking of the photodefinable dielectric composition components to result in the development' of the desired physical and chemical properties of the resultant film, non- limiting examples of such being a low dielectric constant, low moisture uptake properties, low modulus and resistance to chemicals.
• the composition may be partially cured in one processing step and the cure 'completed' in a 1 5 subsequent processing step.
• R 1 , R 2 , R 3 , and R 4 in structural formula I are independently selected from one of the following groups:
• Ci Ci to C 5 linear, branched, and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl, 3.0 and alkynyl containing one or more hetero atoms selected from O, N, and Si;
• A is a -inking group selected from Ci to C 6 linear, branched, and cyclic alkylene and R 23 and R 24 are independently selected from H, methyl, and ethyl;
• R 23 and R 24 are as defined above, and each occurrence of R 21 and R 22 are independently selected from H, methyl, and ethyl;
• R 1 , R 2 , R 3 , and R 4 linked together by a linking group selected from Ci to C 25 linear, branched, and cyclic alkylene and alkylene aryl; wherein n is an integer of from 1 to 25, R 5 is an acid labile group, and R 6 is selected from H, Ci to C 6 linear, branched, and cyclic alkyl, an epoxy containing group of structural formula II
• a portion of the repeat units having structural formula I contain at least one epoxy functional pendant group.
• Such exemplary embodiments can encompass a copolymer containing 65-75 mole % of a first repeat unit of structural formula I, where R 1 , R 2 , and R 3 are H, and R 4 is decyl, and 25-35 mole % of a second repeat unit of structural formula I, wherein R , R , and 0 R 3 are H, and R 4 is an epoxy containing group of structural formula ⁇ , wherein A is methylene and R 23 and R 24 are H.
• any of R 1 , R 2 , R 3 , and R 4 can have a structure according to the formula -(CH 2 ) n C(O)OR 5 , where R 5 is an acid labile group, i.e., a group that will react to from a carboxylic acid group in the presence of acid in a catalytic manner.
• R 5 2 5 can be any suitable acid labile group and includes, but is not limited to, -C(CH 3 ) 3 , -Si(CH 3 )3, -CH(R 7 )CH 2 CH 3 , -CH(R 7 )C(CH 3 ) 3 , dicyclopropylmethyl, dimethylcyclopropyhnethyl, and a compound described by one or more of structural formulas IV - X:
• R 7 is selected from H and Ci to C 6 linear, branched, and cyclic alkyl.
• the copolymer backbone further includes one or more repeat units selected from repeat units having structural units XI-XV:
• R 12 is selected from Ci to C 6 linear, branched, and cyclic alkyl; and R 15 is selected from H and C ⁇ to C linear and branched alkyl.
• the copolymer when the copolymer includes one or more of repeat units XI - XV, those repeat units are present at a level of at least 1 mole %, in some cases at least 2 mole %, and in other cases at least 3 mole % of the copolymer. Also,
• the copolymer includes one or more of repeat units XI - XV at a level of up to 10 mole %, in some cases up to 9 mole %, in other cases up to 7 mole %, and in some situations up to 5 mole %.
• One or more of repeat units XI - XV can be present in the copolymer between any range of values recited above.
• Embodiments of the copolymer encompass repeat units in accordance with structural formula I that contain an epoxy functional group.
• the epoxy groups when suitably catalyzed, crosslink with neighboring epoxy groups to give a crosslinked polymer that is resistant to solvent attack.
• Such repeat units containing epoxy 5 - functional groups are included in the copolymer at a level of at least 20 mole %, in some cases at least 25 mole %, and in other cases at least 35 mole % of the copolymer. Also, the repeat units containing epoxy functional groups are included in the copolymer at a level of up to 95 mole %, in some cases up to 75 mole %, in other cases 60 mole %, in some situations up to 50 mole %, and in other situations up to 35 mole % of the copolymer. The amount of
• epoxy functional . groups. in the copolymer is determined based on the physical properties desired in the copolymer and or photodefinable layers and cured layers containing or derived from the copolymer.
• the amount of epoxy functional groups in the copolymer can vary between any of the values recited above.
• Such copolymer embodiments have excellent physical properties, particularly
• ⁇ 5 for use in photodefinable compositions for electrical or electronic devices.
• low moisture absorption less than 2 weight percent
• low dielectric constant less than 3.9
• low modulus less than 3 GigaPascal (GPa)
• low cure temperature less than 200° Celsius (C)
• good solubility in many common organic solvents for example low moisture absorption (less than 2 weight percent), low dielectric constant (less than 3.9 low modulus (less than 3 GigaPascal (GPa)), low cure temperature (less than 200° Celsius (C)) and good solubility in many common organic solvents.
• the polymer in an examplary embodiment of the present invention, the polymer
• composition is a low K composition.
• the polymer composition, photodefinable dielectric compositions containing the polymer composition, and/or cured layers and or films derived from such photodefinable dielectric compositions have a dielectric constant of less than 3.9.
• the dielectric constant of the polymer composition, photodefinable dielectric compositions containing the polymer composition, and/or cured 5- layers and/or films derived from such photodefinable dielectric compositions are typically at least 2.2, in some cases at least 2.3, and in other cases at least 2.5.
• the dielectric constant of the polymer composition, photodefinable dielectric compositions containing the copolymer, the polymer composition, and/or cured layers and/or films derived from such photodefinable dielectric compositions can be up to 3.3, in some cases up to 2.9, and in other
• the dielectric constant is sufficiently low to provide reduction of transmission delays and alleviation of crosstalk between conductive lines in electrical and/or electronic devices containing the inventive polymer composition.
• the dielectric constant of the copolymer, the polymer composition, photodefinable dielectric compositions containing the polymer composition, and/or cured layers and/or films derived from such photodefinable dielectric compositions can vary between any of the values recited above.
• the modulus of the copolymer, the polymer composition, the photodefinable dielectric compositions containing 5 the copolymer, and/or cured layers and/or films derived from such photodefinable dielectric compositions are typically at least 0.1 GPa, in some cases at least 0.2 GPa, and in other cases at least 0.3 GPa.
• the modulus of the copolymer, the polymer composition, photodefinable dielectric compositions containing the copolymer, and/or cured layers and/or films derived from such photodefinable dielectric compositions can be up to 3 GPa, in some
• compositions can vary between any of the values recited above.
• the polymer compositions are photodefinable dielectric compositions containing polymer compositions and/or cured layers and/or films derived from such photodefinable dielectric compositions that have a moisture absorption of less than 2 weight percent, in some cases less than 0.8 weight percent, and in 0 other cases less than 0.3 weight percent. It will be understood that such embodiments provide for improved resistance to moisture absorption when compared to other previously known photodefinable definable polymeric materials.
• epoxy functional group mole % in the copolymer backbone determines many physical properties of the copolymer and/or photodefinable layers 5. and cured layers containing or derived from the copolymer.
• the copolymer when the copolymer contains from 15 mole % to 95 mole % repeat units containing epoxy groups, the copolymer typically has a moisture absorption of less than 2 weight percent and a dielectric constant of less than 3.3.
• the copolymer includes repeat units containing an epoxy at a level of from 20 mole % to 60 mole %, the
• S 0 copolymer has a moisture absorption of less than 0.8 weight percent and a dielectric constant of less than 2.9; and when the copolymer includes repeat units containing an epoxy at a level of from 25 mole % to 35 mole %, the copolymer has a moisture absorption of less than 0.3 weight percent and a dielectric constant of less than 2.6.
• moisture absorption is determined by measuring weight gain in accordance with ASTM D570-98.
• Copolymers in accordance with the present invention have a glass transition temperature of at least 170°C, in some cases at least 200°C, and in some cases at least 220°C. Also, the inventive copolymer has a glass transition temperature of up to 350°C, in some cases up to 325°C, in other cases up to 300°C, and in some situations up to 280°C.
• the copolymer has a glass transition temperature that allows for processing of the polymer composition, photodefinable compositions containing the copolymer, and cured layers containing the copolymer. As a non-limiting example, the glass, transition temperature is sufficient to allow successful solder reflow during microchip production.
• the glass transition temperature of the copolymer can vary between any of the values indicated above. As referred to herein, the glass transition temperature of the copolymer is determined using Dynamic Mechanical Analysis (DMA) on a Rheometric Scientific Dynamic Analyzer Model RDAII available from TA Instruments, New Castle, DE according to ASTM D5026-95 (temperature: ambient to 400°C at a rate of 5°C per minute).
• DMA Dynamic Mechanical Analysis
• RDAII available from TA Instruments, New Castle, DE according to ASTM D5026-95 (temperature: ambient to 400°C at a rate of 5°C per minute).
• Copolymers in accordance with the present invention have a weight average molecular weight (Mw) of at least 10,000, in some cases at least 30,000, in other cases at least 50,000, in some situations at least 70,000, and in other situations at least 90,000. Also, such copolymers have aMw of up to 500,000, in some cases up to 400,000, in other cases up to 300,000, in some situations up to 250,000, and in other situations up to 140,000. Mw is determined by gel permeation chromatography (GPC) using poly(norbornene) standards. The Mw of the copolymer is sufficient to provide the desired physical properties in the copolymer and/or photodefinable layers and cured layers containing or derived from the copolymer.
• Mw weight average molecular weight
• the polymer composition also includes a solvent selected from reactive and non-reactive compounds.
• the solvent can be one or more of hydrocarbon solvents, aromatic solvents, cyclo aliphatic cyclic ethers, cyclic ethers, acetates, esters, lactones, ketones, amides, aliphatic mono- and multivinyl ethers, cycloaliphatic mono- and multivinyl ethers, aromatic mono- and multivinyl ethers, cyclic carbonates, and mixtures thereof.
• solvents that can be used include cyclohexane, benzene, toluene, xylene, mesitylene, tetrahydrofuran, anisole, terpenenoids, cyclohexene oxide, ⁇ -pinene oxide, 2,2'-[methylenebis(4,l-phenyleneoxymethylene)]bis-oxirane, 1,4- cyclohexanedimethanol divinyl ether, bis(4-vinyloxyphenyl)methane, cyclohexanone, and decalin.
• solvents include cyclohexane, benzene, toluene, xylene, mesitylene, tetrahydrofuran, anisole, terpenenoids, cyclohexene oxide, ⁇ -pinene oxide, 2,2'-[methylenebis(4,l-phenyleneoxymethylene)]bis-oxirane, 1,4- cyclohexanedimethanol divin
• Exemplary embodiments of the present invention encompass polymer compositions that are photonically catalysed negative-working photosensitive polymer compositions useful as a protective coating for substrates used in printing wiring board applications, including redistribution layers for build up multilayer devices and high density interconnect microvia substrates.
• the polymer compositions can be a photodefinable polymer composition that can be applied and patterned as a dielectric layer for the packaging of integrated circuits to protect against environmental and mechanical stresses.
• the photodefinable compositions are useful as redistribution layers, passivation layers, and stress buffer materials for conventional, chip O scale, and wafer level packaging of logic, AppHcation Specific Integrated Circuits (ASICs), discrete, memory, and passive devices.
• ASICs AppHcation Specific Integrated Circuits
• the inventive copolymer can be prepared by vinyl-addition polymerization.
• a monomer composition that includes polycycloolefin monomers as described in structure I and, optionally, structures XI-XV are polymerized in solution in the presence of a desired catalyst.
• Vinyl-addition catalysts useful in preparing the inventive copolymer include nickel and palladium compounds as disclosed in PCT WO 97/33198 and PCT WO 00/20472. 0 * A non-limiting example of a vinyl-addition catalyst useful in making the copolymers utilized in this invention is represented by the formula:
• n' is 1 or 2 and E represents a neutral 2 electron donor ligand.
• E 5 preferably is a pi-arene ligand such as toluene, benzene, and mesitylene.
• E is preferably selected from diethyl ether, THF (tetrahydrofuran), ethyl acetate (EtOAc), and dioxane.
• the ratio of monomer to catalyst in the reaction medium can range from about 5000:1 to about 50:1 in an exemplary embodiment of the invention, and in another exemplary embodiment at a ratio of about 2000:1 to about 100:1.
• the reaction can be run in a suitable O solvent at a temperature range from about 0°C to about 70°C. In an exemplary embodiment, the temperature can range from about 10°C to about 50°C, and in another exemplary embodiment from about 20°C to about 40°C.
• Catalysts of the above formula that can be used to make the inventive copolymers include, but are not limited to,
• Suitable polymerization solvents for the free radical and vinyl addition polymerization reactions include, but are not limited to, hydrocarbon and aromatic solvents.
• Hydrocarbon solvents useful in the invention include, but are not limited to, to alkanes and cycloalkanes such as pentane, hexane, heptane, and cyclohexane.
• Non-limiting examples of aromatic solvents include benzene, toluene, xylene, and mesitylene.
• Other organic solvents such as diethyl ether, tetrahydrofuran, acetates, e.g., ethyl acetate, esters, lactones, ketones, O and amides are also useful. Mixtures of one or more of the foregoing solvents can be utilized as a polymerization solvent.
• the molecular weight of the polymer can be controlled by employing a molecular weight modifying agent such as is disclosed in U.S. Patent No. 6,136,499, the disclosure of which is herein incorporated by reference in its entirety.
• a molecular weight modifying agent such as is disclosed in U.S. Patent No. 6,136,499, the disclosure of which is herein incorporated by reference in its entirety.
• ethylene, propylene, 1-hexene, 1-decene, and 4-methyl-l-pentene are suitable for molecular weight control.
• exemplary embodiments of the present invention are also directed to photodefinable dielectric compositions that include an embodiment of the copolymer and a material that photonically forms a catalyst.
• Any suitable material that photonically forms a catalyst can be used in the present invention.
• suitable materials that form a catalyst photonically include photoacid generators and photobase generators.
• the photoacid generator can include one or more compounds selected from onium salts, halogen-containing compounds, and sulfonates.
• the photoacid generator includes one or more compounds selected from 4,4'-ditertiarybutylphenyl iodonium triflate; • 4,4',4"-tris(tertiary butylphenyl)sulphonium triflate; diphenyliodonium tetrakis(pentafluorophenyl)sulphonium borate; triarylsulphonium- 0 tetrakis(pentafluorophenyl)-borate; triphenylsulfonium tetrakis(pentafluorophenyl)sulphonium borate; 4,4'-ditertiarybutylphenyl iodonium tetrakis(p
• Such photoacid generators are present at a level sufficient to promote curing and crosslinking.
• photoacid generators are employed in the photodefinable dielectric composition, such are present in an amount of at least 0.5 percent by weight, in some cases at least 0.75 percent by weight, and in other cases at least 1 percent by weight- of the photodefinable dielectric composition.
• the photoacid generator is present in an amount of up to 10 percent by weight, in some cases up to 7.5 percent by weight, and in other cases up to 5 percent by weight of the photodefinable dielectric O composition.
• the amount of photoacid generator present in the photodefinable dielectric composition can vary between any of the values recited above.
• Embodiments of copolymers in accordance with the present invention are present in the photodefinable dielectric composition at a level sufficient to provide the above- described desired physical properties to the resulting composition, as well as coated layers 5 and cured layers formed from the photodefinable dielectric composition.
• the embodiment of the copolymer is present in the photodefinable dielectric composition in an amount of at least 5 percent by weight, in some cases at least 15 percent by weight, and in other cases at least 25 percent by weight of the photodefinable dielectric composition.
• the copolymer is present in the photodefinable dielectric composition in an amount of up to 65 percent by weight, in some cases up to 60 percent by weight, and in other cases up to 55 percent by weight of the photodefinable dielectric composition.
• the amount of the copolymer embodiment present in the photodefinable dielectric composition can vary between any of the values recited above.
• exemplary embodiments of the present invention can include other suitable components and/or materials such as are necessary for formulating and using the photodefinable dielectric compositions in accordance with the present invention.
• Such other suitable components and/or materials include one or more components selected from sensitizer components, solvents, catalyst scavengers, adhesion promoters, antioxidants, fire retardants, stabilizers, reactive diluents, and plasticizers.
• any suitable sensitizer component can be included in the photodefinable dielectric compositions of the present invention.
• sensitizer components include, but are not limited to, anthracenes, phenanthrenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes, xanthones, indanthrenes, thioxanthen-9-ones, and mixtures thereof.
• suitable sensitizer components include 2-isopropyl-9H-thioxanthen-9-one, 4-isopropyl-9H-fhioxanthen-9-one, l-chloro-4- propoxythioxanthone, phenothiazine, and mixtures thereof.
• Li exemplary embodiments of the present invention having both a material that photonically forms a catalyst and a sensitizer component can be present in the photodefinable dielectric composition in an amount of at least 0.1 percent by weight, in some cases at least 0.5 percent by weight, and in other cases at least 1 percent by weight of the photodefinable dielectric composition.
• the sensitizer component is present in the photodefinable dielectric composition
• photodefinable dielectric composition in an amount of up to 10 percent by weight, in some cases up to 7.5 percent by weight, and in other cases up to 5 percent by weight of the photodefinable dielectric composition.
• the amount of sensitizer component present in the photodefinable dielectric composition in this exemplary embodiment can vary between any of the values recited above.
• a catalyst scavenger When used emodiments of the photodefinable dielectric composition, it can include an acid scavenger and/or a base scavenger.
• Non-limiting examples of acid scavengers that can be used in the present invention include secondary amines and/or tertiary amines such as those selected from pyridine, phenothiazine, tri(n-propyl amine), triethylamine, and lutidine in any of its isomeric forms.
• the latter can be present in the photodefinable dielectric composition in an amount of at least 0.1 percent by weight, in some cases at least 0.25 percent by weight, and in other cases at least 0.5 percent by weight of the photodefinable dielectric composition.
• the catalyst scavenger is present in the photodefinable dielectric composition in an amount of up to 5 percent by weight, in some cases up to 4 percent by weight, and in other cases up to 3.5 percent by weight, of the photodefinable dielectric composition.
• the solvent includes suitable reactive and/or non-reactive compounds.
• suitable solvent compounds include, but are not limited to, hydrocarbon solvents, aromatic solvents, cycloaliphatic cyclic ethers, cyclic ethers, acetates, esters, lactones, ketones, amides, cycloaliphatic vinyl ethers, aromatic vinyl ethers, cyclic carbonates and mixtures thereof.
• the suitable solvent compounds include one or more of cyclohexane, benzene, toluene, xylene, mesitylene, tetrahy ⁇ rofuran, anisole, cyclohexene oxide, ⁇ -pinene oxide, 2,2'-[methylenebis(4,l-phenyleneoxymethylene)]bis-oxirane, 1,4-cyclohexanedimethanol divinyl ether, bis(4-vinyloxyphenyl)methane, cyclohexanone, and decalin.
• the solvent is present in the photodefinable dielectric composition in an amount of at least 20 percent by weight, in some cases at least 30 percent by weight, in other cases at least 40 percent by weight, in some situations at least 45 percent by weight, and in other situations at least 50 percent by weight of the photodefinable dielectric composition.
• the solvent is present in an amount sufficient O to provide desired rheological properties, a non-limiting example being viscosity, to the photodefinable dielectric composition.
• the solvent is present in the photodefinable dielectric composition in an amount of up to 95 percent by weight, in some cases up to 80 percent by weight, in other cases up to 70 percent by weight, and in some situations up to 60 percent by weight of the photodefinable dielectric composition.
• the amount of solvent 5 present in the photodefinable dielectric composition in this exemplary embodiment can vary between any of the values recited above.
• adhesion promoter any suitable adhesion promoter can be used in the present invention. Suitable adhesion promoters improve the bond strength between a coated layer of photodefinable dielectric composition and the substrate upon which it is coated.
• the adhesion promoter includes one or more compounds selected from 3-aminopropyl triethoxysilane and compounds described by structural unit XVI:
• z Si — R 5 — O-CH2— ⁇ - ⁇ ( ⁇ vI) wherein z is 0, 1, or 2;
• R 8 is a linking group selected from to C 2 o linear, branched, and cyclic alkylene, alkylene oxide containing from 2 to 6 carbon atoms, and poly(alkylene oxide), wherein the alkylene portion of the repeat groups contains from 2 to 6 carbon atoms and .
• the poly(alkyiene oxide) has a molecular weight of from 50 to 1,000; each occurrence of R 9 is independently selected from Ci to C 4 linear and branched alkyl; and each occurrence of R 18 is selected from H and Ci to C linear and branched alkyl.
• any suitable reactive diluent can be used in the present invention. Suitable reactive diluents improve one or more of the physical properties of the photodefinable dielectric composition and or coating layers formed from the photodefinable dielectric composition.
• the reactive diluents include one or more . compounds selected from epoxides and compounds described by structural units XVH and XVTH:
• R 10 is a linking group selected from to C 2 o linear, branched, and cyclic alkylene, arylene and alkylene aryl, alkylene oxide containing from 2 to 6 carbon atoms, poly(alkylene oxide), wherein the alkylene portion of the repeat groups contain from 2 to 6 carbon atoms and the poly(alkylene oxide) has a molecular weight of from 50 to 1,000, -[-R 13 -N-C(O)-O-] m - R 13 -, wherein each occurrence of R 13 is independently selected from C ⁇ to C 2 o linear, branched, and cyclic alkylene, arylene, and alkylene aryl, and m is an integer of from 1 to 20; and 11 is selected from Ci to C 20 linear and branched, alkyl, and alkylol.
• the reactive diluents include one or more reactive diluents selected from 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,8- octanediol divinyl ether, 1,4-dimethanolcyclohexane divinyl ether, 1,2-ethylene glycol divinyl ether, 1,3-propylene glycol divinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 1,4-butanediol vinyl ether, 1,6-hexanediol vinyl ether, and 1,8-octanediol vinyl ether.
• the reactive diluent is present in the photodefinable dielectric composition in an amount of at least 0.5 percent by weight, in some cases at least 1 percent by weight, in other cases at least 2.5 percent by weight, in some situations at least 5 percent by weight, and in other situations at least 7.5 percent by weight of the photodefinable dielectric composition.
• the reactive diluent is present in an amount sufficient to provide desired physical properties to the photodefinable dielectric composition and coating layers formed from the photodefinable dielectric composition.
• the reactive diluent is present in the photodefinable dielectric composition in an amount of up to 95 percent by weight, in some cases up to 60 percent by weight, in other cases up to 30 percent by weight, and in some situations as little as 1 percent by weight of the photodefinable dielectric composition.
• the amount of reactive diluent present in the photodefinable dielectric composition in this exemplary embodiment can vary between any of the values recited above.
• the photodefinable dielectric composition When the photodefinable dielectric composition includes a solvent and/or a reactive diluent, the photodefinable dielectric composition is in a fluid liquid solution form.
• the solution viscosity of the photodefinable dielectric composition is at least 10 centipoise (cps), in some cases at least 100 cps, and in other cases at least 500 cps.
• the solution viscosity of the photodefinable dielectric composition is up to 25,000 cps, in some cases up to 20,000 cps, in other cases up to 15,000 cps, in some situations up to 10,000 cps, in other situations up to 5,000 cps, and in some circumstances up to 3,000 cps.
• the solution viscosity is determined at 25°C using a suitable spindle on a Brookfield DV-E viscometer, available from Brookfield Engineering Laboratories, Middleboro, MA.
• the viscosity of an amount of the photodefinable dielectric composition in this exemplary embodiment can vary between any of the values recited above.
• An exemplary embodiment of the present invention is directed to a method of forming a photodefinable layer on a substrate.
• the method includes the steps of providing a substrate, coating at least one side of the substrate with the photodefinable dielectric composition described above, exposing the coated layer to radiation, and curing the radiation-exposed layer.
• Any suitable method of coating may be used to coat the substrate with the photodefinable dielectric composition.
• suitable coating methods include, but are not limited to, spin coatmg, dip coating, brush coating, roller coating, spray coating, solution casting, fluidized bed deposition, extrusion coating, curtain coating, meniscus coating, screen or stencil printing and the like.
• spin coating and curtain coating are used because of their simplicity and high uniformity.
• Cast films from this embodiment of the photodefinable dielectric composition have superior properties such as toughness, craze resistance to solvents, infrequent pinhole defe'cts, excellent planarity, and adhesion among other properties.
• the coated layer can be exposed using any suitable source of energy for exposure. Suitable sources include radiation.
• Non-hmiting examples of radiation sources include, but are not limited to, photon radiation and or an electron beam.
• the photon radiation is ultraviolet radiation at a wavelength of from 200 nm to 700 nm, in some cases 300 nm to 500 nm, and in other cases from 360 nm to 440 nm.
• the dose of radiation for exposing is from 50 mJ/cm 2 to
• the method of forming a photodefinable layer on a substrate includes the step of defining a pattern in the cured layer.
• the pattern can be defined by imagewise exposing the layer.
• when the layer is imagewise exposed it is typically imaged through a photomask by photon radiation, non-limiting examples of which include electron beam, x-ray, ultraviolet, or visible radiation. Suitable radiation sources include mercury, mercury/xenon, xenon lamps, rF laser, x-ray, or e-beam.
• Imagewise exposure of the photodefinable dielectric composition of the invention can be accomplished at many different wavelengths as indicated above.
• the sensitizer or photoacid generator becomes active, inducing the formation of a free acid.
• the free acid catalyzes the crosslinking of the pendant epoxy groups on the polymer backbone, in turn, converting the photon-patterned areas of the 0 polymer from a solvent soluble state to a solvent insoluble state.
• the soluble areas are easily removed with an appropriate solvent developer.
• the method of forming a photodefinable layer on a substrate includes the step of developing the layer.
• Any suitable solvent developer may 5 be used in the present invention.
• Suitable developers are those that are able to remove the soluble portion of the cured layer fo ⁇ ned from the photodefinable dielectric composition.
• Suitable developers include, but are not h ited to, toluene, mesitylene, xylene, decalin, limonene and BioAct EC-7R (a limonene based solvent composition formulated with surfactants) available from Petroferm, Inc., Fernandina Beach, FL.
• Any suitable solvent development method can be used in the present invention.
• suitable solvent development methods include, but are not limited to, spray, puddle, and/or immersion techniques.
• Spray development includes the step of spraying the patterned polymer coated substrate with a continuous stream of atomized or otherwise dispersed stream of developing solvent for a period of time sufficient 5 to remove the non-crosslinked polymer from the substrate.
• the polymer coated substrate can be subjected to a final rinse with an appropriate solvent such as an alcohol.
• the puddle and immersion technique involves puddling developing solvent over the entire patterned coating or immersing the patterned coated substrate into developing solvent to dissolve the non-crosslinked polymer, and then rinsing the developed substrate in additional developing O solvent or another appropriate solvent (e.g., an alcohol).
• the developed coated substrate can be spun at high speed to remove residual solvent and solute.
• the present method of forming a photodefinable layer on a substrate includes a curing step.
• the curing step follows
• the curing step can include a bake cycle.
• the bake cycle can increase the reaction rate of the epoxy crosslinking reaction.
• the acid species from the photoacid generators have increased mobility during the cure cycle, allowing the acid to find and react with non-crosslinked epoxy functionality, thereby further enhancing the pattern definition.
• the curing step is conducted in an oven under inert atmosphere (e.g., nitrogen, argon, or helium) at a temperature of from about 50°C to 200°C for a period of time between 5 minutes and 60 minutes; or from about 100°C to about 150°C for a period of time between 10 minutes and 40 minutes; or from about 110°C to about 130°C for between 15 minutes and 30 minutes; or from about 90°C to about 200°C for a period of from 1 minute to 60 minutes.
• inert atmosphere e.g., nitrogen, argon, or helium
• the layer When the photodefinable layer has been exposed to radiation and cured, the layer is in the form of a film covering at least a portion of a surface of the substrate.
• the fihn may have any suitable film thickness, typically determined to provide for the number, orientation, and configuration of conducting lines in the photodefined product.
• films formed as described above have a thickness of at least 0.1 microns, in some cases at least 0.2 microns, and in other cases at least 0.5 microns.
• films formed according to the present invention have a thickness of up to 500 microns, in some cases up to 400 microns, in other cases up to 300 microns, in some situations up to 250 microns, in other situations up to 200 microns, in some circumstances up to 100 microns, and in other circumstances up to 50 microns.
• film thickness is a function of solution concentration, spin speed, and time in spin coating.
• the film thickness of the radiation exposed and cured photodefinable layer in this exemplary embodiment can vary between any of the values recited above.
• the softbake cycle is employed to remove residual solvents.
• the softbake cycle also relaxes stress resulting from the flow of the photodefinable layer fihn, increases the film's adhesion to the substrate, and hardens the film for more convenient handling during processing.
• the softbake cycle is carried out under any suitable conditions. Suitable conditions include those sufficient to remove residual solvent, but able to avoid oxidizing or thermal curing of the resin or undesired reactions of the formulation additives, and which, allows the resin to flow sufficiently to promote planarization. The conditions will vary depending in part on the components of the polymer containing formulation.
• Suitable softbake conditions include, but are not limited to, temperatures of at least 90°C, in some cases at least 100°C, and in other cases at least 110°C and up to 140°C, in some cases up to 130°C, and in other cases up to 120°C for at least 1 minute, in some cases at least 2 minutes, in other cases at least 5 minutes and up to 30 minutes, in some cases up to 20 minutes, and in other cases up to 10 minutes.
• the softbake can be performed in a convection oven, belt oven, or on a hot plate- Suitable 5 softbake atmospheres include a vacuum, solvent vapor, air, and inert gas atmosphere such as nitrogen, argon, and helium.
• the method includes includes a final cure step.
• the solvent developed coated substrate is post baked in an oven under inert atmosphere (e.g., nitrogen, 0 argon, or helium) at a temperature ranging from about 50°C to about 200°C, and in some cases 100°C to 200°C to achieve a final cure and to remove any residual developing and/or rinsing solvent.
• inert atmosphere e.g., nitrogen, 0 argon, or helium
• including a blanket exposure of the layer as part of the final cure step is effective in achieving the final cure.
• such exposure is in addition to the thermal post bake and has is of a range of energies from about 1 5 200mJ to about 500mJ, inclusive.
• the crosslinking reaction is completed as the thermosetting epoxy polymer continues to react.
• the glass transition temperature of the crosslinked polymer film has been 0 increased from 180°C to greater than 250°C.
• the final glass transition temperature of a fhermoset polymer is typically equivalent to the cure temperature used for the final cure. This is due to the limitations of molecular mobility as the curing polymer changes from a rubbery solid to a glassy solid at the Tg.
• a significant advantage of the present photodefinable compositions is that the final cure temperature is 5 below the Tg of the uncrosslinked polymer solid, and yet an increase in the Tg of up to 70°C is observed by dynamic mechanical analysis (DMA)- after the crosslinking reaction is completed.
• DMA dynamic mechanical analysis
• a polymer composition layer is formed by steps including providing a substrate, fixing a film to the substrate by depositing a solution containing a material that photonically forms a catalyst and the inventive polymer composition, and thermally curing the solution.
• the method can include a softbaking step as described above.
• the entire film is thermally crosslinked.
• Selected feature definitions are subsequently patterned into the crosslinked fihn by a suitable etching technique, such as, for example, reactive ion etching (RLE.) or laser ablation at selected wavelengths.
• the thermal crosslinking reaction is initiated by a thermal curing agent which generates an acid upon thermal activation.
• the thermally generated acid in turn catalyzes the crosslinking reaction of the epoxy functionality.
• the thermal curing agents or thermal acid generators include many of the photacid generators set forth above. In O addition to photo-activation, it is well known that photoacid generators can be activated at elevated temperatures. Generally, the activation temperatures range from about 25°C to about 250°C.
• Suitable thermal acid generators include the onium salts, halogen containing compounds and sulfonates set forth above. It should be apparent to those skilled in the art that any thermally activated initiator can be employed so long as it is capable of initiating a 5 crosslinking reaction of the epoxy functionality on the polymer backbone. Examples of such thermal curing agents or thermal acid generators include, but are not limited to, imidazoles, primary, secondary, and tertiary amines, quaternary ammonium salts, anhydrides, polysulfides, polymercaptans, phenols, carboxylic acids, polyamides, quaternary phosphonium saits, and combinations thereof.
• coated, patterned, developed, and cured films of the present invention have superior properties such as a low dielectric constant, low moisture absorption, toughness, craze resistance to solvents, and adhesion among other properties.
• Polymer films with at least some of these.properties are useful in the fabrication of microelectronic devices where high-density packaging, interconnection, and fine features such as microvias are required.
• the electrical and/or electronic O devices are semiconductor devices.
• the electrical or electronic devices are selected from a logic chip, a passive device, a memory chip, a microelectromechanical system (MEMS) chip, a microoptoelectromechanical systems (MOEMS) chip, and an application specific integrated circuit (ASIC) chip.
• MEMS microelectromechanical system
• MOEMS microoptoelectromechanical systems
• ASIC application specific integrated circuit
• This example illustrates the synthesis of a 70/30 copolymer polymerized from decyl norbornene/glycidyl methyl ether norbornene). All glassware was dried at 60° C under a 0.1 torr vacuum for 18 hours. The glassware was then transferred into a glovebox and the reaction vessel was assembled inside the glovebox. Ethyl acetate (917g), cyclohexane
• the dry glassware was transferred into a glove box and the reaction vessel was assembled inside the glove box.
• Toluene (670g), decyl norbornene (29.43g, 0.144 mol), glycidyl methyl ether norbornene (16.6g, 0.212 mol) were added to the IL reaction vessel.
• the reaction vessel was removed from the glove box and connected to a dry nitrogen line.
• the reaction solution was degassed by passing a stream of nitrogen gas through the solution for 30 minutes.
• the catalyst was prepared by dissolving 0.00189g (allyl)palladium(tricyclohexylphosphine)trifluoroacetate (756 g/mol) in 0.4 mL of methylene chloride resulting in 0.00625 Molar solution.
• the cocatalyst was prepared by dissolving O.Ollg lithium tetrakis(pentafluorophenyl)borate (875 g/mol) into 25g of toluene resulting in a 457x10 " ° mol/mL solution.
• the reagent 1-hexene was added as a chain transfer agent for purposes of controlling molecular weight, in the portions indicated in the table below.
• solvents, monomers, catalysts, and cocatalyst were added in the following order: TABLE I
• GE-NB glycidyl methyl ether norbornene
• LiFABA lithium tetrakis(pentafluorophenyl)borate
• Pd Catalyst (allyl)palladium(tricyclohexylphosphine)trifluoroacetate
• the sample vial was crimp capped under nitrogen, and placed in a fumehood where it was immersed in a silicon oil bath K at 30° C to stir for 4.5 hours.
• the samples were then opened, and precipitated by adding the viscous solution in a dropwise manner, to methanol.
• the resulting solid is filtered through a size M glass frit funnel.
• the precipitated polymer was dissolved in toluene, and precipitated into methanol.
• the precipitated polymer was recovered by filtration and dried under vacuum for 18 hours at 70° C and weighed. .
• the bottle was sealed with a Teflon® lined crimp cap and the bottle was removed to a fumehood.
• the reaction medium was degassed by bubbling dry nitrogen gas through the solution for 10 minutes.
• (0.0973g, 0.20 mmol) of bis(toluene)bis(perfluorophenyl) nickel catalyst was dissolved in 3.3 mL of toluene, taken up in a 10 mL syringe, removed from the glove box and injected into the reaction vial.
• the reaction mixture was stirred at ambient temperature for 48 hours.
• To the reaction bottle was added 0.56g of Amberlite® IRC-718 ion-exchange resin available from the Rohm and Haas Company and the solution was mixed for a further 5 hours.
• the resin was removed by filtration.
• the polymer was precipitated into 100 mL of methanol and recovered by filtration.
• the precipitated polymer 0 was washed with 25 mL of methanol and the dried in a vacuum oven at 60° C for 18 hours. l.SOg (47 % yield) of dry polymer was recovered.
• the reaction vessel was removed from the glove box and connected to a dry nitrogen line.
• the reaction solution was degassed by passing a stream of nitrogen gas through the solution for 30 minutes.
• 1.80g (4.1 mmol) of bis(toluene)bis(perfluorophenyl) nickel catalyst was dissolved in 8 ml of toluene, taken up in a 10 mL syringe, removed from the glove box and injected into the reactor .
• the reaction was stirred at 20°C for 1 hour. At this time 180 g of
• a 65/25/1 Ocopolymer prepared from hexyl norbornene/glycidyl methyl ether norbomene/t-butyl ester norbornene was synthesized in the following manner. All glassware was dried at 160° C for 18 hours. The dry glassware was transferred into a glove box and the reaction vessel was assembled inside the glove box. Toluene (750g), hexyl norbornene
• Ethyl acetate (280g), cyclohexane (280g), decyl norbornene (34.7g, 0.16 mol), glycidyl methyl ether norbornene (39.6g, 0.22 mol) and triethoxysilylnorbornene (2.56g, 0.01 mol) were added to the reaction vessel.
• the reaction vessel was removed from the glove box and connected to a dry nitrogen line.
• the reaction solution was degassed by passing a stream of nitrogen gas through the solution for 30 minutes.
• the resin beads were removed by filtration and the polymer was then precipitated by addition into methanol.
• a solid polymer was 5 recovered by filtration and dried overnight at 60°C in a vacuum oven. 55.0g of dry polymer (76 % conversion) was recovered after drying.
• the polydispersity index was 2.9.
• a polymer solution was prepared using the 256.5 g of the polymer obtained in Example 2.
• the polymer was placed into a 1 -liter wide mouth glass bottle and 313.5g of electronic grade mesitylene was added.
• the bottle was sealed with a Teflon® lined polyethylene cap and the polymer was uniformly dispersed by rolling the bottle at 50 rpm for
• the polymer solution was filtered through a 0.45 micron Teflon® filter to remove any particulate matter. This operation was performed under a laminar flow hood in a class 1000 clean room. The filtered polymer solution was collected in a class 1000 clean room bottle. The final concentration of the polymer in solution was determined by gravimetric analysis to be 45.0 wt. %. 20.0g of polymer solution was weighed into a 50-mL amber clean
• Rhodorsil® PI 2074 (4- methylphenyl-4-(l methylethyl)phenyliodonium tetiakis(pentafluorophenyl)borate) available from Rhodia. (0.2757g, 2.71 x 10-4 mol), SpeedCure® CPTX l-chloro-4-propoxy-9H- thioxanthone available from Lambson Group Inc.
• a polymer solution was prepared using the 228.0 g of the polymer obtained in Example 2. The polymer was placed into a 1-liter wide mouth glass bottle and 342.0g of decahydronaphthalene was added. The bottle was sealed with a Teflon® lined polyethylene cap and the polymer was uniformly dispersed by rolling the bottle at 50 rpm for 18 hours. The polymer solution was filtered through a 0.45 micron Teflon® filter to remove any particulate matter. This operation was performed under a laminar flow hood in a class 1000 clean room. The filtered polymer solution was collected in a clean (0 particles greater than
• a polymer solution was prepared as set forth in Example 9. 20.0g of the polymer solution containing the polymer synthesized in Example 1 (45.0 wt. % solids) was
• Rhodorsil® PI 2074 (4-methylphenyl-4-(l ' methylethyl)phenyliodonium tetrakis(pentafiuorophenyl)borate) (0.184g, 0.181 mmol), Isopropyl-9H-thioxanthen-9-one
• the materials were dissolved into 5.0g of anisole and the solution was filtered through a 0.22-micron syringe filter as it was added to ' the polymer solution. The solution was rolled at 50 rpm for 18 hours to disperse the additives in the polymer solution.
• a polymer solution was prepared as set forth in Example 11. 20. Og of the polymer solution containing the polymer synthesized in Example 2 (40.0 wt. % solids) was weighed into a 50-mL amber clean room bottle. Formulation additives were weighed 0 out separately into 10-mL beakers and then dissolved in 5.0g of anisole. The additives were
• Rhodorsil® PI 2074 (4-methylphenyl-4-(l methylethyl)phenyliodonium . tetrakis(pentafluorophenyl)borate) (0.184g, 0.181 mmol), Isopropyl-9H-thioxanthen-9-one (FirstCure ITX 0.046g, 0.181 mmol), phenothiazine (Aldrich Chemical Co.
• a polymer solution was prepared as set forth in Example 9. 20.0g of the polymer solution containing the polymer synthesized in Example 1 (45.0 wt. % solids) was weighed into a 50 L amber clean room bottle. Formulation additives were weighed out separately into 10 mL beakers and then dissolved in 5.0g of anisole.
• the additives were DTBPI-TF di(4-tertbutylphenyl)Iodonium triflate (PAG) (0.2757g, 5.08 x 10 "4 mol) (Toyo Gosei Kogyo Tokyo), 9-methoxyanthracene (sensitizer) (0.1378g, 6.62 x 10 "4 mol), and Irganox® 1076 antioxidant (0.1378g, 2.60 x 10 "4 mol) (CIBA Fine Chemicals).
• the materials were dissolved into 5.0g of mesitylene and the solution was filtered through a 0.22 micron syringe filter as it was added to the polymer solution. The solution was rolled at 50 rpm for 18 hours to disperse the additives in the polymer solution.
• a polymer solution was prepared as set forth in Example 9. 72.8 lg of the polymer solution containing the polymer synthesized in Example 2 (45.0 weight % solution) was weighed into a lOOmL amber clean room bottle. Formulation additives were weighed 5 out separately into 10-mL beakers and then dissolved in 5.0g of anisole. The additives were
• Rhodorsil® PI 2074 (4-methylphenyl-4-(l methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate) (1.6251g, 1.587 mmol), l-chloro-4-propoxy-9H- thioxanthone (SpeedCure CPTX 0.4837g, 1.587 mmol), and Irganox® 1076 antioxidant (CIBA Fine Chemicals) (0.1378g, 2.60 x 10 "4 mol).
• the materials were dissolved into 5.0g O of anisole and the solution was filtered through a 0.22-micron syringe filter as it was added to the polymer solution. To this solution was added the reactive solvent 1,4- cyclohexanedimethanol divinyl ether (3.205g, 0.166 mol). The solution was rolled at 50 rpm for 18 hours to disperse the additives in the polymer solution.
• a 2.5g aliquot of the composition described in Example 9 was taken up in an Eppendorf pipette and applied to a 4 inch Silicon wafer.
• the silicon wafer was spun using a O CEE lOOOCB Wafer Spin Station at 500 rpm for 10 seconds followed by spinning at 1000 rpm for 60 seconds.
• the wafer was placed on a hot plate heated at 100° C for 10 minutes to flash off the residual solvent.
• the wafer was imagewise exposed to 500 mJ/cm at 365nm radiation through a patterned chrome plated glass mask on an AB M Mask Aligner.
• the wafer was heated at 100° C for 20 minutes in a Despatch LND nitrogen oven to advance the 5 crosslinking reaction in the exposed regions of the polymer film.
• the pattern was developed by puddling the wafer under 20 mL of a limonene based solvent for 60 seconds, spinning the wafer at 3000 rpm for 60 seconds to remove the solvent puddle and then spraying the wafer with isopropyl alcohol for 10 seconds to fix the pattern.
• the wafer was then placed in a Despatch LND nitrogen oven and baked at 200° C in order to complete the crosslinking reaction.
• the 5 wafer was heated at 115° C for 15 minutes in a Despatch LND nitrogen oven to advance the crosslinking reaction in the exposed regions of the polymer film.
• the pattern was developed by puddling the wafer under 20 mL of a limonene based solvent for 60 seconds, spinning the wafer at 3000 rpm for 60 seconds to remove the solvent puddle and then spraying the wafer with isopropyl alcohol for 10 seconds to fix the pattern.
• the wafer was then placed in a 0 Despatch LND nitrogen oven and baked at 160°C for 60 minutes in order to complete the crosshnking reaction.
• Eppendorf pipette and applied to a 4 inch Silicon wafer The silicon wafer was spun using a CEE lOOOCB Wafer Spin Station at 500 rpm for 10 seconds followed by spiiining at 1000 rpm for 60 seconds. The wafer was placed on a hot plate heated at 100° C for 10 minutes to flash off the residual solvent. The wafer was imagewise exposed to 500 mmJ/cm 2 at 365nm 0 radiation through a patterned chrome plated glass mask on an AB M Mask Aligner. The wafer was heated at 100°C for 20 minutes in a Despatch LND nitrogen oven to advance the crosslinking reaction in the exposed regions of the polymer film.
• the pattern was developed by puddling the wafer under 20 mL of a limonene based solvent for 60 seconds, spinning the wafer at 3000 rpm for 60 seconds to remove the solvent puddle and then spraying the wafer with isopropyl alcohol for 10 seconds to fix the pattern.
• the wafer was then placed in a Despatch LND nitrogen oven and baked at 200° C in order to complete the crosslinking reaction.
• a silicon oxynitride coated 4 inch silicon wafer was plasma treated in a March CS-1701 Reactive Ion Etch unit using a 50/50 Argon/oxygen gas mixture at 300 mTorr pressure and 300W power for 30 seconds.
• the cleaned wafer was placed on the chuck of a CEE lOOOCB Wafer Spin Station and covered with a 10 mL aliquot of a solution of an adhesion promoter (3-aminopropyl triethoxysilane) (5 weight % in ethanol /deionized water 95/5).
• the wafer was kept static (0 rpm) for 60 seconds and the spun at 3500 rpm for 60 seconds to remove the excess solution.
• the wafer was baked on a hot plate at 130° C for 30 minutes, removed from the hot plate, rinsed with ethanol for 15 seconds and then dried at
• Example 9 100° C for 10 minutes.
• a 2.5g aliquot of the resist composition described in Example 9 was taken up in an Eppendorf pipette and applied to a 4 inch Silicon wafer.
• the silicon wafer was spun using a CEE lOOOCB Wafer Spin Station at 500 rpm for 10 seconds followed by spinning at 1000 rpm for 60 seconds.
• the wafer was placed on a hot plate heated at 100° C for 10 minutes to flash off the residual solvent.
• the wafer was imagewise exposed to 500 mJ/cm 2 at 365nm radiation through a patterned chrome plated glass mask on an AB M Mask Aligner.
• the wafer was heated at 100° C for 20 minutes in a Despatch LND nitrogen oven to advance the crosslinking reaction in the exposed regions of the polymer film.
• the pattern was developed by puddling the wafer under 20 mL of a limonene based solvent for 60 seconds, spinning the wafer at 3000 rpm for 60 seconds to remove the solvent puddle and then spraying the wafer with isopropyl alcohol for 10 seconds to fix the pattern.
• the wafer was then placed in a Despatch LND nitrogen oven and baked at 200° C in order to complete the crosslinking reaction.
• the wafer was heated at 115°C for 15 minutes in a Despatch LND nitrogen oven to advance the crosshnking reaction in the exposed regions of the polymer film.
• the pattern was developed by puddling the wafer under 20 mL of a limonene based solvent for 60 seconds, spinning the wafer at 3000 rpm for 60 seconds to remove the solvent puddle and then spraying the wafer with isopropyl alcohol for 10 seconds to fix the pattern.
• the wafer was then placed in a Despatch LND nitrogen oven and baked at 160°C for 60 minutes in order to complete the crosslinking reaction.
• a resist composition is formulated and imaged using the same procedures, ingredients and amounts as set forth in Example 19.
• the pattern is developed by spraying the wafer with the limonene based developer for 60 seconds and then, with isopropyl alcohol for 10 seconds.
• the sample is cured at 200°C as set forth above.
• EXAMPLE 22 This example demonstrates that the polymers contained in the compositions of the present invention can be cured at a temperature below the Tg of the polymer.
• a composition was formulated, imaged and developed as set forth in Example 19. The final cure was carried out in a Despatch LND nitrogen oven at 160° C for 1 hour.
• the polymer contained in the formulation had a Tg of 180 ° C as measured by DMA.
• the polymer exhibited a Tg of approximately 255° C after the final cure.
• EXAMPLE 23 A resist composition was formulated, imaged and developed as set forth in Example 15. The entire polymer film was then exposed to 500 mJ/cm 2 of 365nm UV radiation in a non-imagewise manner to induce the additional crosslinking of any unreacted epoxy groups. A final cure was carried out in a Despatch LND nitrogen oven at 120° C for 2 hours. After curing the polymer exhibited a Tg of approximately 257° C.
• EXAMPLE 24 Imaging of Photodefinable Composition
• a composition was formulated as set forth in Example 15. The photodefinable polymer composition was imaged and developed using the same procedures as set forth in Example 19.
• the pattern was developed by spraying the wafer with the limonene based developer for 60 seconds and then with isopropyl alcohol for 10 seconds.
• the imaged and developed polymer sample was then exposed to 500 mJ/cm2 of 365nm UV radiation.
• the sample was cured at 120°C for 1 hour in a Despatch LND nitrogen oven.
• Example 9 the composition set forth in Example 9 was applied to a silicon wafer as follows.
• the wafer is placed on a flat, leveled table and fixed in place with masking tape.
• a doctor blade with a nominal gap of 12 mils (300 microns) was placed adjacent to the wafer.
• 15mL of the solution was applied to one edge of the wafer.
• the doctor blade is drawn across the wafer to uniformly spread the solution across the wafer surface.
• the wafers were placed in a nitrogen oven set at 90° C and allowed to dry for 45 minutes.
• the wafers were then exposed imagewise to 500 mJ/cm 2 of 365nm UV radiation through a chrome plated glass mask.
• the wafers were returned to the nitrogen oven and baked at 90°C for 20 minutes to advance the crosslinking reaction.
• the pattem was developed by spraying the wafer for 90 seconds with a limonene-based developer solvent.
• the film was rinsed with isopropyl alcohol for 15 seconds to fix the image.
• a grid pattern of 300 micron diameter circular vias was opened in the fihn.
• Example 9 a composition formulated as set forth in Example 9, was applied to two silicon oxynitride coated silicon wafers and exposed imagewise to 500 mJ/cm 2 of 365nm radiation in the manner described in Example 16. The exposed wafers were then processed as follows:
• the pattem was then developed by spraying the wafer with a limonene based developer for 60 seconds and then rinsing with isopropyl alcohol for 10 seconds to fix the pattern.
• the Wafers were then baked in a nitrogen oven for 1 hour at 160° C to complete the crosslinking reaction.
• a pattern of 300 micron diameter circular vias was developed in the dielectric film. .
• the wafers were broken so that Scanning Electron Microscopy could be performed. Through SEM imaging, the slope angles of the sidewalls of the 300 micron vias were measured and recorded as follows:
• Example 26 a composition is formulated, imaged and developed using the same procedures, ingredients and amounts as set forth in Example 26, except that the polymer synthesized in Example 4 is employed as the photodefinable material.
• EXAMPLE 30 Imaging of a polymer film formulated and cast from the polymer obtained in Example 9 was performed on a 4 inch diameter silicon oxynitride wafer. The wafer was subjected to successive rinses (30 seconds each) with chloroform, methanol, deionized water, and isopropyl alcohol. Each of the solvent rinses was delivered from a polyethylene wash bottle.
• the polymer (25g) obtained in Example 9 was dissolved in 30.5g of mesitylene (Aldrich Chemical Co.) to achieve a 45 % solids concentration based on the total weight of the polymer and solvent. 0.50g (0.92 mmol)of DtBPI-TF di(tertbutylphenyl)iodonium triflate PAG (Toyo Gosei Co. Ltd.) and 0.25g (1.2 mmol) of 9- methoxyanthracene where weighed out and dissolved in 5 mL of mesitylene. The solution resulting solution was filtered thorough a 0.22 micron syringe filter before addition to the polymer solution.
• mesitylene Aldrich Chemical Co.
• the solution containing the photoactive compounds was rolled for 18 hours to completely disperse the constituents.
• the polymer solution was applied to the cleaned wafer by dispensing 2.5 grams of the solution onto the wafer surface.
• the wafer was then spun at 500 rpm for ten seconds, followed by an addition spin cycle at 1000 rpm for 60 seconds.
• the wafer was soft baked on a hot plate at 100° C for 10 minutes to remove residual solvent.
• the cast polymer film was exposed imagewise to 500 mJ/cm 2 of 365-nm radiation through a chrome metal plated glass mask.
• the cure was advanced by thermally baking the wafer in a convection oven at 100° C for 20 minutes under an atmosphere of nitrogen gas.
• the pattern was then developed puddling the wafer with a limonene based developer solvent for 60 seconds.
• the wafer was spun at 3000 rpm to throw off the solvent and partially dry the sample.
• the developed film was then rinsed with ' isopropyl alcohol and dried by heating on a hot plate at
• Example 30 was formulated except that a 70/30 copolymer containing repeating units polymerized from decyl norbornene/glycidyl methyl ether norbornene was utilized.
• a solvent rinsed silicon oxynitride wafer was exposed to an oxygen/argon plasma (50/50) for sixty seconds in a March CS-1701 R.I.E. Plasma Etcher powered by a Seren R600 operating at 13.56 MHz. The etched wafer was then mounted on the spin chuck of a Brewer Science
• Model 100CB spinner A solution of adhesion promoter (prepared by dissolving a 10ml ahquot of 3-aminopropyl triethoxysilane in 200ml of ethanol/deionized water (95/5) solution and aged for 1 hour at ambient temperature) was applied to the wafer by puddling 15 ml of the solution on the wafer surface and holding the wafer static for sixty seconds. The wafer was then spun at 3500 rpm for sixty seconds. During the first fifteen seconds of the spin cycle the wafer surface was rinsed with 50 ml of an ethanol/water (95/5) solution. The wafer was then dried on a hot plate at 100°C for sixty seconds.
• adhesion promoter prepared by dissolving a 10ml ahquot of 3-aminopropyl triethoxysilane in 200ml of ethanol/deionized water (95/5) solution and aged for 1 hour at ambient temperature
• the solution was applied to the treated wafer by dispensing 2 g of the solution onto the static wafer surface.
• the wafer was then spun at 500 rpm for ten seconds followed by an additional spin cycle at 1500 rpm for forty seconds.
• the wafer was transferred to a hot plate where it was soft baked at 100° C for 20 minutes to remove residual solvent.
• the resulting polymer film was measured by profilometry and found to be 25 microns thick.
• the polymer film was patterned by exposing it to 500 mJ/cm of 365nm radiation through a metallized glass mask. The pattern was advanced by thermally b-iking the wafer in a convection oven at 100° C for 20 minutes under an atmosphere of nitrogen gas.
• the film was sprayed with a limonene based developer solvent for 60 seconds to develop the pattern.
• the wet fihn was then rinsed with isopropyl alcohol and dried by heating on a hot plate for 60 seconds at 100° C.
• the developed pattern gave 50 to 300 ⁇ M via openings with a resolution down to an aspect ratio of 2:1 via diameter: film thickness.
• the patterned film was then cured at 200° C for 1 hour in a convection oven under an atmosphere of nitrogen in order to advance the cure of the epoxy crosslinking groups to completion.
• Example 32 (Imaging of Photodefinable Composition) The same composition utilized in Example 32 was applied to applied to a. silicon oxynitride wafer and imaged utilizing the same procedures set forth in Example 32 except that the wafer was treated with a different adhesion promoter.
• a 2-micron thick layer of a photosensitive polyimide (PI 2771 available from HD Microsystems) was applied to the wafer surface, patterned, developed and cured according to the processing guidelines for the polyimide material.
• the wafer was exposed to an oxygen/argon plasma (50/50 feed ratio) using a 96 sccm/second feed rate, for sixty seconds.
• the patterned, developed and cured coating contained 50 to 300 ⁇ M via openings with a resolution down to an aspect ratio of 2:1 via diameter : film thickness. - . •

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