WO2000061667A1 - Polymeres a squelettes dotes de groupes reactifs utilises dans la reticulation comme precurseurs de structures a films fins nanoporeux - Google Patents

Polymeres a squelettes dotes de groupes reactifs utilises dans la reticulation comme precurseurs de structures a films fins nanoporeux Download PDF

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WO2000061667A1
WO2000061667A1 PCT/US2000/009168 US0009168W WO0061667A1 WO 2000061667 A1 WO2000061667 A1 WO 2000061667A1 US 0009168 W US0009168 W US 0009168W WO 0061667 A1 WO0061667 A1 WO 0061667A1
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reactive groups
crosslinking
backbone
polymeric strands
difluoroaromatic
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PCT/US2000/009168
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English (en)
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Kreisler Lau
Roger Leung
Tian-An Chen
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Alliedsignal Inc.
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Priority to AU40764/00A priority Critical patent/AU4076400A/en
Priority to KR1020017012886A priority patent/KR20020060068A/ko
Priority to EP00920186A priority patent/EP1171516A1/fr
Priority to JP2000611602A priority patent/JP2003520864A/ja
Publication of WO2000061667A1 publication Critical patent/WO2000061667A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/046—Elimination of a polymeric phase
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/034—Organic insulating material consisting of one material containing halogen

Definitions

  • the field of the invention is nanoporous materials. Background As the size of functional elements in integrated circuits decreases, complexity and interconnectivity increases. To accommodate the growing demand of interconnections in modern integrated circuits, on-chip interconnections have been developed. Such interconnections generally consist of multiple layers of metallic conductor lines embedded in low dielectric constant materials. The dielectric constant in such materials has a very important influence on the performance of an integrated circuit. Materials having low dielectric constants (i.e., below 2.2) are desirable because they allow faster signal velocity and shorter cycle times. Moreover, lowering of the dielectric constant reduces capacitive effects, leading often to less cross talk between conductor lines and lower voltages to drive integrated circuits.
  • One way of achieving low dielectric constants in the insulator materials is to employ materials with inherently low dielectric constants.
  • materials with inherently low dielectric constants Two different classes of low dielectric constant materials have been employed in recent years - inorganic oxides and organic polymers.
  • Inorganic oxides often have dielectric constants between 3 and 4, and have been widely used in interconnects with design rules larger than 0.25 ⁇ m. As the dimensions of the interconnects shrink, materials with a lower dielectric constant become more desirable.
  • Organic polymers have shown many advantageous properties including high thermal stability, ease of processing, low stress/TCE, low dielectric constant and high resistance, and are therefore considered as alternative low dielectric constant polymers for the 0.18 ⁇ m and subsequent generations of increasingly smaller dimensions.
  • desirable dielectrics should also be free from moisture and out-gassing problems, have suitable adhesive and gap-filling qualities, and have suitable dimensional stability towards thermal cycling, etching, and CMP processes (i.e., chemical mechanical polishing). Suitable dielectrics should also have Tg values (glass transition temperatures) of at least 300°C, and preferably 500°C or more.
  • thermostable polymer is blended with a thermolabile (thermally decomposable) polymer.
  • the blended mixture is then crosslinked and the thermolabile portion thermolyzed. Examples are set forth in U.S. Pat. No. 5,776,990 to Hedrick et al.
  • thermolabile blocks and thermostable blocks alternate in a single block copolymer.
  • the block copolymer is then heated to thermolyze the thermolabile blocks.
  • thermostable blocks and thermostable blocks carrying thermolabile portions are mixed and polymerized to yield a copolymer.
  • the copolymer is subsequently heated to thermolyze the thermolabile blocks.
  • small hollow glass spheres are introduced into a material. Examples are given in U.S. Pat. 5,458,709 to Kamezaki and U.S. Pat. 5,593,526 to Yokouchi.
  • thermostable portions in nanoporous materials.
  • specific crosslinking functionalities are already incorporated into the polymer.
  • Such functionalities react together to crosslink polymers prior to thermolysis of the thermolabile portion.
  • it is known to include a tolanyl function in a block copolymer and to use the ethynyl functions to crosslink polyimide polymers.
  • This is depicted graphically in prior art Figure 1, in which two independent polymeric strands 10 A, 10B carry crosslinking functionalities XI and X2 as pendent groups, and thermolabile portions L as both pendent groups and as part of the backbones.
  • XI and X2 react to form crosslinks Y, thereby covalently connecting the two strands 10A, 10B into a single crosslinked polymer IOC.
  • exogenous crosslinking molecules are employed in crosslinking.
  • the crosslinked polymer is then heated to thermolyze the thermolabile portion.
  • aromatic monomers are crosslinked using exogenously added multifunctional acyl- or benzylic halides. This is depicted graphically in prior art Figure 2, in which two independent polymeric strands 20A, 20B again carry crosslinking functionalities XI and X2 as pendent groups, and thermolabile portions L as both pendent groups and as part of the backbones.
  • XI and X2 react with an exogenous crosslinking molecule X3, thereby forming crosslinks Y, and covalently connecting the two strands 20A, 20B into a single crosslinked polymer 20C.
  • thermostable portions in nanoporous materials has significant limitations.
  • the use of exogenous crosslinking molecules requires that the crosslinkers specifically react with the thermostable portion without interfering with the polymerization reaction.
  • the crosslinkers must be soluble in the same solvent system as the blockpolymers or monomers. Therefore, the chemical structure and reactivity of the thermostable portion and thermolabile portion frequently dictate the nature of the exogenous crosslinking molecules.
  • Another limitation is that the use of "built-in" specific crosslinking functionalities in a polymer increases the complexity of the polymer, thereby often compounding difficulties in the synthesis of monomers.
  • the present invention provides methods and compositions in which nanoporous materials are fabricated from fluorinated and nonfluorinated polymers having backbones with flexible structural moieties and with reactive groups used in crosslinking.
  • the reactive groups in the backbone comprise a diene and a dienophile.
  • the diene comprises a tetracyclone and the dienophile comprises an ethynyl in the form of a tolanyl.
  • the reactive groups in the backbone are included in a conjugated system.
  • the polymeric strands comprise a fluorinated poly(arylene ether) synthesized from a fluorinated difluoroaromatic portion and a fluorinated aromatic bisphenolic portion.
  • the difluoroaromatic portions of the poly(arylene ether) are modified in such a way, that some difluoroaromatic portions carry a thermolabile portion.
  • crosslinking occurs without reliance on an exogenous crosslinker.
  • Figure 1 is a prior art scheme depicting crosslinking of polymeric strands containing thermolabile groups.
  • Figure 2 is a prior art scheme depicting crosslinking of polymeric strands containing thermolabile groups, using an exogenous crosslinking molecule.
  • Figure 3 is a scheme depicting crosslinking of polymeric strands containing thermolabile groups according to one aspect of the inventive subject matter.
  • Figure 4 is a scheme depicting crosslinking of polymeric strands containing thermolabile groups according to another aspect of the inventive subject matter.
  • Figure 5 is a general synthetic scheme for fabricating poly(arylene ethers).
  • Figures 6A - 6J are structures of contemplated difluoroaromatic compounds according to the inventive subject matter.
  • Figure 7 is a synthetic scheme for producing a tetracyclone containing arylene ether polymer.
  • Figure 8 is a synthetic scheme for grafting a thermally labile component to a polymeric strand.
  • Figures 9 A and 9B are structures of difluoroaromatic monomers that lead to tetracyclone-containing poly(arylene ethers) according to the inventive subject matter.
  • Figures 10 and 11 are structures of difluoroaromatic monomers that lead to tetracyclone-and ethynyl-containing poly(arylene ethers) according to the inventive subject matter.
  • Figures 12A-12I are structures of repeating portions in a polymeric strand according to the inventive subject matter.
  • two polymeric strands 30A, 30B carry a plurality of thermolabile groups L.
  • Each of the polymeric strands defines a backbone, and each of the backbones includes reactive groups Xi and X 2 .
  • Strands 30A and 30B are crosslinked in a crosslinking reaction between reactive groups Xi and X 2 without addition of an exogenous crosslinking molecule. The crosslinking reaction results in crosslinks Z, thereby covalently connecting, or possibly further connecting strands 30A, 30B to form polymer 30C.
  • the thermolabile groups L are thermolyzed, leaving voids. When the voids are sufficiently small and sufficiently well distributed, the resulting material thus becomes a nanoporous polymer.
  • Figure 4 is quite similar to Figure 3, except that reactive group Xi forms part of the backbone in strand 40A, while reactive group X 2 is pendent to the backbone in strand 40B. Nevertheless, the crosslinking reactions proceed, resulting in crosslinks Z and a crosslinked polymer 40C.
  • polymeric strand refers to any composition of monomers covalently bound to define a backbone, and may include any pendant groups other than those coupled via crosslinking.
  • monomer refers to any chemical compound that is capable of forming a covalent bond with itself or a chemically different compound in a repetitive manner.
  • the repetitive bond formation between monomers may lead to a linear, branched, super-branched or three-dimensional product.
  • Monomers may belong to various chemical classes of molecules including organic, organometallic or inorganic molecules. Examples of organic monomers are acrylamide, vinyl chloride, fluorene bisphenol or 3,3'-dihydroxytolane. Examples of organosilicon monomers are octa- methylcyclotetrasiloxane, methylphenylcyclotetrasiloxane, etc.
  • inorganic monomers that lead to inorganic SiO 2 or Al 2 O 3 structures include the most commonly used tetraethoxysilane (TEOS) and aluminum ethoxide.
  • TEOS tetraethoxysilane
  • the molecular weight of monomers may vary greatly between about 40 Dalton and 20000 Dalton.
  • Monomers may also include thermolabile groups or functionalities for crosslinking.
  • monomers may comprise poly(propylene oxide), polycarbonates, poly(methylmethacrylate), various styrenic polymers, or ethynyl- or tetracyclone groups. It is also contemplated that monomers may be halogenated, whereby a prefe ⁇ ed halogen is fluorine. Halogenation, and especially fluorination may advantageously reduce the dielectric constant of the monomer, and indirectly reduce the dielectric constant of the nanoporous polymer.
  • polymeric strands may thus be linear, branched, super- branched, or three-dimensional, and may include thermolabile portions and reactive groups.
  • Polymeric strands may belong to any chemical class, including organic or inorganic compositions. Examples of organic polymeric strands are polyimides, polyesters, or polybenzils. Examples of organosilicon polymeric strands are various substituted polysiloxanes. Examples of inorganic polymeric strands include silica or alumina. Polymeric strands may also comprise a wide range of functional or structural moieties, including aromatic systems, and halogenated groups, including a fluorine atom, or a -CF 3 group. Polymeric strands may also have additional reactive groups capable of participating in a chemical reaction. The molecular weight of contemplated polymeric strands span a wide range, typically between 400 Dalton and 400000 Dalton or more.
  • Especially prefe ⁇ ed polymeric strands are those having a ring system, and having backbone crosslinking groups comprising a diene and a dienophile.
  • a particularly prefe ⁇ ed class comprises strands in which the diene is the cyclopentadienone of a tetracyclone.
  • Such strands can advantageously comprise fluorinated or non- fluorinated polybenzils, and can be prepared from a fluorinated or non-fluorinated difluoroaromatic compound and a fluorinated or nonfluorinated aromatic bisphenolic compound.
  • the aromatic bisphenolic compound comprises a fluorene bisphenol
  • the difluoroaromatic compound comprises a tolane.
  • the difluoroaromatic compound comprises a tetracyclone.
  • prefe ⁇ ed embodiments may be characterized by a modification of the aromatic portion of the aromatic bisphenolic compound, or modification of the aromatic portion of the difluoroaromatic compound.
  • modifications may include isomeric variations, or addition or removal of aromatic groups.
  • a tetracyclone, halogens, amides, alcohols, aliphatic or aromatic substituents may be introduced into an aromatic portion of a 3,3'-dihydroxytolane.
  • Analogous changes are also contemplated for the aromatic portion of a 4,4'-difluorobenzil.
  • an sp 2 - hybridized carbon atom may be replaced by any other appropriate atom, including sulfur, oxygen, nitrogen, etc.
  • the modification comprises an introduction of a halogen, and especially a fluorine
  • one or more than one fluorine atom can be covalently bound to an aromatic carbon atom, or that one or more than one fluorine atom may be covalently bound to a non-aromatic carbon atom.
  • at least one fluorine atom may also be covalently bound to a non-aromatic carbon atom while at least one fluorine atom may be covalently bound to an aromatic carbon atom.
  • the polymeric strands may be completely different from a polybenzil.
  • Alternative polymeric strands include organic, organometallic or inorganic polymers. Examples of contemplated organic polymers are polyimides, polyesters and polycyanurates. Examples of contemplated organometallic polymers are poly(dimethylsiloxane) and poly(vinylsiloxane). Examples of contemplated inorganic polymers are polysilicates and polyaluminates. Indeed, contemplated polymeric strands need not comprise a single type of monomer, but may comprise a mixture of various non-identical monomers.
  • backbone refers to a contiguous chain of atoms or moieties forming a polymeric strand are covalently bound such that removal of any of the atoms or moiety would result in interruption of the chain.
  • Prefe ⁇ ed backbones comprise an aromatic ring system, or at least a conjugated group.
  • contemplated backbones may include any elements, including especially C, N, O, S, P, Si, and Al.
  • contemplated backbones may include aromatic groups including phenyl-, substituted or unsubstituted cyclopentadienyl groups, thermolabile groups, aromatic ring systems, and fluorinated or other reactive groups.
  • crosslinking refers to a process, in which at least two molecules, or two portions of a long molecule, are joined together by a chemical interaction. Such interactions may occur in many different ways including formation of a covalent bond, formation of hydrogen bonds, hydrophobic, hydrophilic, ionic or electrostatic interaction. Furthermore, molecular interaction may also be characterized by an at least temporary physical connection between at least one molecule with itself or between two or more molecules. Therefore, it is contemplated that a polymeric strand according to the inventive subject matter may crosslink with itself. . Crosslinking is typically mediated by various reactive groups, and may occur by numerous mechanisms.
  • a covalent bond is formed between two reactive groups, it may be formed by a variety of chemical reaction mechanisms, including additions, eliminations or substitutions. Examples are nucleophilic or electrophilic addition, El- or E2- type eliminations, nucleophilic and aromatic substitutions.
  • Crosslinking may be a spontaneous process or may require energy or a catalyst. Examples of such energy are thermal energy, radiation, mechanic, electric or electromagnetic energy. Examples of catalysts are acids, bases, and palladium-coated activated charcoal.
  • crosslinking may or may not involve extrinsic crosslinkers, and any extrinsic crosslinker may comprise single molecules, crosslinking molecules may also themselves be oligomeric or even polymeric.
  • the number of reactive groups in a strand that are used for crosslinking may vary widely. This would typically depend on the strength of crosslinking required, as well the strength of the individual crosslinking links. For example, to form a stable crosslink at room temperature between two single strands of nucleic acids, a minimum of about 25-30 hydrogen bonds is required. In contrast, only one covalent bond is needed to achieve a crosslink with even higher stability. It is also contemplated that the number of reactive groups participating in crosslinking may vary within a wide range. For example, crosslinking may involve as little as 5% of reactive groups, but may also involve more than 90% of all available reactive groups in the polymeric strands. Although prefe ⁇ ed reactive groups are not identical to one another, it is also contemplated that all of the reactive groups may be identical to one another.
  • reactive group refers to any elements or combinations of elements having sufficient reactivity to be used in crosslinking or coupling with a pendent group. Reactive groups are contemplated to be positioned in any part of a backbone, including the termini. In prefe ⁇ ed embodiments, the diene may comprise a tetracyclone and the dienophile may comprise an ethynyl group. In other embodiments, alternative reactive groups may include nucleophilic or electrophilic centers.
  • thermostable refers to the tendency of a material to resist elevated temperatures, typically in the range of 300°C to 450°C.
  • the thermostable portion of the polymer comprises a polybenzil.
  • the polybenzil is prepared from a difluoroaromatic compound and an aromatic bisphenolic compound, wherein both compounds may be fluorinated.
  • the aromatic bisphenolic compound comprises a fluorene bisphenol
  • the difluoroaromatic compound comprises a tolane.
  • the difluoroaromatic compound comprises a tetracyclone.
  • thermolabile refers to the property of a material to degrade above an elevated temperature, typically in the range of 250°C to 400°C. It should be understood that the thermolabile groups of Figures 3 and 4 may be positioned in any part of the backbones, including the termini.
  • Prefe ⁇ ed thermolabile groups include polypropyleneoxide, polylactides, polycarbonates or polymethylmethacrylate.
  • the thermolabile portion is attached to a polybenzil polymer within a difluoroaromatic portion in the polymeric chain, and comprises an ethylene glycol-poly(caprolactone).
  • at least 5-25% of the difluoroaromatic portion carries an ethylene glycol-poly(caprolactone) with an average molecular weight of 3000 Dalton.
  • Thermolabile groups L may advantageously include a connector moiety.
  • the size of the connector moiety may vary considerably from molecular weights of about 20 Dalton to about and above 500 Dalton. Examples of relatively small connector moieties are acidic groups, basic groups, nucleophilic groups and electrophilic groups.
  • Alternative small connector moieties are, for example, R-CO 2 H, R-CO-R', R-NH 2 , R-SH, R- Halogen and so on.
  • larger connector moieties are tetracyclones, cyclopentadiene groups or bifunctional aliphatic groups, including especially 1,2- diaminobenzenes or l,3-diphenylpropan-2-ones.
  • alternative connector moieties need not have a single type of functional group or single type of substituent, but alternative connector moieties may also be a mixture of various non-identical connector moieties. It is further contemplated that alternative connector moieties need not engage in formation of a covalent bond.
  • Appropriate alternative connectors may also engage in non-covalent coupling including hydrophobic-, electrostatic- ionic interactions, complex formation or hydrogen bonding.
  • Examples are leucine zipper-like structures, highly polar groups, polycationic groups or polyanionic groups, and polydentate-type groups.
  • Connector moieties may also be located in any part of the thermolabile group including the termini.
  • the term "degrade” as used herein refers to the breaking of covalent bonds. Such breaking of bonds may occur in many ways, including heterolytic, radical, and homolytic breakage. The breaking of bonds need not be complete, i.e. not all breakable bonds must be cleaved. Furthermore, the breaking of bonds may occur in some bonds faster than in others. Ester bonds, for example, are generally less stable than amid bonds, and are therefore cleaved at a faster rate. Breakage of bonds may also result in the release of fragments differing from one another, depending on the chemical composition of the degraded portion.
  • the energy involved in thermolysis may comprise thermal, electromagnetic, mechanical energy, particulate or non-particulate radiation. For example, an appropriate energy could be alpha-radiation, sonication, microwaves or heating.
  • thermolabile portion a polymeric strand wherein each of the polymeric strands includes a thermolabile portion, and defines a backbone including a plurality of reactive groups; providing a first energy to crosslink the polymeric strands using at least one of the reactive groups; and providing a second energy to at least partially degrade the thermolabile portion.
  • nanoporous material refers to any material that includes a significant number of voids with diameters in a range of about 1 nm to about 1000 nm.
  • Contemplated compositions for nanoporous materials include synthetic polymers, inorganic material, and organosilicon compounds.
  • synthetic polymers are polyethers, polyimides or polyesters.
  • inorganic material include silica or aluminosilicates as well as ceramic materials.
  • organosilicon compounds include poly(dimethylsiloxane), poly(vinyl- siloxane) and poly(trifluoropropylsiloxane).
  • Nanoporous materials may be characterized by the extent to which mass is replaced with a gas.
  • the composition of the gas is generally not critical, and appropriate gases include relatively pure gases and mixtures thereof. Air (which is predominantly a mixture of N 2 and O 2 ) is commonly disposed in the "voids" of nanoporous materials, but pure gases such as nitrogen, helium, argon, CO 2 or CO are also contemplated.
  • Nanoporous materials may also be characterized by the structure of the voids. Nanoporous materials typically include spherical voids, but may alternatively or additionally include tubular, lamellar, discoidal, and voids having other shapes. Moreover, some of the voids in nanoporous material may be substantially larger or smaller than about l ⁇ m. Nanoporous materials may have many different forms, including but not limited to thin films, plates, spheres, blocks or cylinders. Nanoporous materials may also comprise additional materials, including fillers, surfactants and plasticizers.
  • the energy preferably comprises a thermal energy, and in particular embodiments is used to heat the strands to about 250°C for 30min.
  • the first energy is preferably sufficient to involve at least 20% of all available reactive groups in the crosslinking. Heating, however, may alternatively involve any suitable temperatures, including temperatures between 150°C and 250°C. In further alternative embodiments, the period of heating may vary greatly, from a few seconds or less, to several hours or more.
  • the first energy need not be thermal energy, but may involve any suitable form of energy including various electromagnetic radiations (e.g., are UN-, laser-, X-rays or infrared i ⁇ adiation), mechanical energy (e.g. sonication or physical pressure), and particle radiation (e.g., alpha- or beta- radiation).
  • the energy is again preferably a thermal energy.
  • such heating may advantageously reach a temperature of about 350°C for approximately 20 minutes.
  • the temperature may vary considerably, depending on the nature of the thermolabile and thermostable portion of the crosslinked polymeric chains. Contemplated temperatures range from 200°C or less, to about 450°C or more.
  • the time required to degrade the thermolabile portion is contemplated to vary greatly from less than a few seconds to at least several hours. Once again it is contemplated that the energy employed may vary from purely thermal energy.
  • nanoporous polymers described herein are similar in some respects to those described in U.S. Pat. no. 5,874,516 to Burgoyne et al. (Feb. 1999), incorporated herein by reference, and may be used in substantially the same manner as set forth in that patent.
  • nanoporous polymers described herein may be employed in fabricating multichip modules, interlayer dielectrics, protective coatings, and as a substrate in circuit boards or printed wiring boards.
  • films or coatings of the nanoporous polymers described herein can be formed by solution techniques such as spraying, spin coating or casting, with spin coating being prefe ⁇ ed.
  • Prefe ⁇ ed solvents are 2-ethoxyethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, chlorobenzene, N-methyl py ⁇ olidinone, N,N-dimethylformamide, N,N-dimethylacetamide, methyl isobutyl ketone, 2-methoxyethyl ether, 5-methyl-2-hexanone, ⁇ -butyrolactone, and mixtures thereof.
  • the coating thickness is between about 0.1 to about 15 microns. As a dielectric interlayer, the film thickness is less than 2 microns.
  • Additives can also be used to enhance or impart particular target properties, as is conventionally known in the polymer art, including stabilizers, flame retardants, pigments, plasticizers, surfactants, and the like. Compatible or non-compatible polymers can be blended in to give a desired property. Adhesion promoters can also be used. Such promoters are typified by hexamethyidisilazane, which can be used to interact with available hydroxyl functionality that may be present on a surface, such as silicon dioxide, that was exposed to moisture or humidity. Polymers for microelectronic applications desirably contain low levels (generally less than 1 ppm, preferably less than 10 ppb) of ionic impurities, particularly for dielectric interlayers. Examples
  • AR and AR 1 can independently comprise any suitable thermally stable structure with a preponderance of aromatic or fused aromatic portions, and in the examples in Figure 5 HO-CfjH -AR-C 6 H -OH is fluorene bisphenol, and F-CeH -AR 1 - C ⁇ $ H 4 -F is a difluoroaromatic compound containing at least one tolane moiety.
  • a general synthetic procedure for the nucleophilic aromatic substitution as exemplified by a reaction between fluorene bisphenol and 4-fluoro-3'-(4- fluorobenzoyl)tolane is as follows: IL 3-neck RB flask, equipped with an magnetic sti ⁇ er, a thermocouple, a Dean-Stark trap, a reflux condenser and N 2 inlet-outlet connection was purged by N 2 for several hours and fed with 0.2L warm sulfolane.
  • the temperature was reduced to 165°C, 4-fluorobenzophenone was added and end-capping was continued for 5 hours.
  • the reaction mass was diluted with 165mL of NMP and left for overnight. Then cold reaction mass was filtered through paper filter, precipitated in 5 x MeOH (0.03% HNO 3 ), redisolved in NMP and reprecipitated in 5 x MeOH (0.01% HNO 3 ).
  • the precipitate was filtered using paper filter, washed on filter 3 times each with IL of MeOH and dried in vacuum oven for overnight at 60°-70°C.
  • Figures 6A - 6J are exemplary structures of difluoroaromatic compounds. These novel compositions are particularly advantageous in having flexible structural moieties built into the uncured poly(ar lene ethers), thereby maintaining the polymers' flexibility, low melt viscosities, and high solubilities in common solvents, such as cyclohexanone and benign aromatic ethers such as anisole and phenetole, to facilitate solution formulation and spin-coating.
  • a homogeneous physical blend of any of these compounds with a fluorene bisphenol can be spun onto the surface of a silicon wafer or other target surface, and then thermally activated to undergo a polymerizing and cross- linking reaction, thereby forming a thermally stable network at a temperature lower than 300 °C.
  • thermolabile groups are grafted on (e.g., as set forth in Figure 4), and the resulting polymer is heated further, the thermolabile groups decompose, volatilize and generate voids in the network.
  • the resulting network possesses high glass-transition temperature in excess of 400 °C by virtue of the crosslinking reaction and its high- temperature polymer structural characteristics.
  • a general synthetic scheme for the structures depicted in Figure 6 A and 6B is as follows:
  • Figure 7 depicts a synthetic scheme for producing a tetracyclone containing poly(aryiene ether).
  • a successful polymerization was run at 1 0-160°C for 24 hr, and the polymer was worked up using the same procedure as for other poly(arylene ethers).
  • the tetracyclone containing polymeric product is magenta red in color and possesses a final Mn of 3,000, Mw of 5,600, Mp of 5,200 with PD of 1.9.
  • the molecular weights can be improved by running the polymerization straight at 160°C for 24 hr instead of at 140- 160°C for 24 hr.
  • moderate molecular weight species may be more advantageous due to potentially more effective cross-linking of the polymer with FLARE polymers during curing to form sexiphenylene structures with relatively low density.
  • Figure 8 is a synthetic scheme including general reaction conditions for grafting a thermally labile component to a polymeric strand, in which 4-fluoro-4'- hydroxybenzophenone is reacted in THF (DEAD, PPh 3 ) with ethylene glycol-poly(capro- lactone) to produce a 4-fluorobenzophenone endcapped thermolabile polymer.
  • the thermolabile 4-fluorobenzophenone endcapped thermolabile polymer can then be incorporated into a poly(arylene ether) together with an aromatic bisphenolic compound.
  • Figures 9A and 9B are contemplated structures of difluoroaromatic monomers that lead to tetracyclone-containing poly(arylene ethers).
  • thermoly labilizable units are combined into single polymeric strands.
  • the thermally labile unit mentioned above can be grafted onto the polymer.
  • the polymerization can be conducted with both the 4-fluorobenzoylphenyl-end-capped thermally labile unit and the difluoroaromatic monomer being allowed to react with fluorene bisphenol.
  • Example 6 In Figures 12A-12I, various structures of fluorinated repeating portions in a polymeric strand are shown.
  • the introduction of fluorine into the polymeric strands is especially advantageous, because the dielectric constant of the dielectric material can be tailored according to the specific demands of a particular application.
  • fluorine may directly be incorporated into the backbone by a covalent bond to an aromatic ring system to generate a fluoroaromatic polymeric strand.
  • the fluorine may be added to the backbone in form of a -CF 3 group that may be attached to an aromatic or non-aromatic carbon atom.
  • Fluorine is generally incorporated into the polymeric strands by employing fluorinated bisphenolic compounds and/or highly fluorinated aromatic compoxmds following the general protocol as depicted in Figure 5.

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne des matériaux nanoporeux obtenus à partir de polymères à squelettes dotés de groupes réactifs utilisés dans la réticulation. Selon un procédé et des compositions préférés, les groupes réactifs du squelette comprennent un diène et un diénophile. Le diène peut renfermer un tétracyclone et le diénophile peut renfermer un éthynyle. Selon d'autres variantes préférées, les groupes réactifs du squelette sont compris dans un système conjugué. Des chaînes de polymères préférées comprennent un poly(arylène éther) synthétisé à partir d'une partie difluoroaromatique et d'une partie bisphénolique aromatique. On modifie de préférence les parties difluoroaromatiques du poly(arylène éther) de manière que certaines parties difluoroaromatiques supportent une partie thermolabile. Selon d'autres variantes encore, la réticulation peut se produire sans dépendre d'un réticulateur exogène.
PCT/US2000/009168 1999-04-09 2000-04-07 Polymeres a squelettes dotes de groupes reactifs utilises dans la reticulation comme precurseurs de structures a films fins nanoporeux WO2000061667A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU40764/00A AU4076400A (en) 1999-04-09 2000-04-07 Polymers having backbones with reactive groups employed in crosslinking as precursors to nanoporous thin film structures
KR1020017012886A KR20020060068A (ko) 1999-04-09 2000-04-07 나노 크기의 다공성 박막 구조에 대한 전구체로서가교결합에 이용되는 반응성 기를 구비한 주쇄를 가진중합체
EP00920186A EP1171516A1 (fr) 1999-04-09 2000-04-07 Polymeres a squelettes dotes de groupes reactifs utilises dans la reticulation comme precurseurs de structures a films fins nanoporeux
JP2000611602A JP2003520864A (ja) 1999-04-09 2000-04-07 ナノ多孔質薄膜構造への前駆体として架橋に用いられる反応性基を有する骨格を持ったポリマー

Applications Claiming Priority (3)

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US12845699P 1999-04-09 1999-04-09
US60/128,456 1999-04-09
US53827600A 2000-03-30 2000-03-30

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WO2000061667A1 true WO2000061667A1 (fr) 2000-10-19

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Cited By (5)

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WO2004113427A2 (fr) * 2003-06-06 2004-12-29 Dow Global Technologies Inc. Stratifies nanoporeux
US9109080B2 (en) 2012-10-22 2015-08-18 Delsper LP Cross-linked organic polymer compositions and methods for controlling cross-linking reaction rate and of modifying same to enhance processability
US9109075B2 (en) 2013-03-15 2015-08-18 Delsper LP Cross-linked organic polymers for use as elastomers in high temperature applications
US9127138B2 (en) 2013-01-28 2015-09-08 Delsper LP Anti-extrusion compositions for sealing and wear components
WO2020097009A1 (fr) * 2018-11-05 2020-05-14 University Of Houston System Nouvelles nanoparticules et nanoréseaux formés à partir de celles-ci

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004113427A2 (fr) * 2003-06-06 2004-12-29 Dow Global Technologies Inc. Stratifies nanoporeux
WO2004113427A3 (fr) * 2003-06-06 2005-04-28 Dow Global Technologies Inc Stratifies nanoporeux
EP2792705A3 (fr) * 2003-06-06 2014-11-05 Dow Global Technologies LLC Stratifiés nanoporeux
US9109080B2 (en) 2012-10-22 2015-08-18 Delsper LP Cross-linked organic polymer compositions and methods for controlling cross-linking reaction rate and of modifying same to enhance processability
US9127138B2 (en) 2013-01-28 2015-09-08 Delsper LP Anti-extrusion compositions for sealing and wear components
US9475938B2 (en) 2013-01-28 2016-10-25 Delsper, Lp Anti-extrusion compositions for sealing and wear components
US9109075B2 (en) 2013-03-15 2015-08-18 Delsper LP Cross-linked organic polymers for use as elastomers in high temperature applications
WO2020097009A1 (fr) * 2018-11-05 2020-05-14 University Of Houston System Nouvelles nanoparticules et nanoréseaux formés à partir de celles-ci

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AU4076400A (en) 2000-11-14

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