EP1461370A1 - Compositions organiques - Google Patents

Compositions organiques

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Publication number
EP1461370A1
EP1461370A1 EP01994423A EP01994423A EP1461370A1 EP 1461370 A1 EP1461370 A1 EP 1461370A1 EP 01994423 A EP01994423 A EP 01994423A EP 01994423 A EP01994423 A EP 01994423A EP 1461370 A1 EP1461370 A1 EP 1461370A1
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EP
European Patent Office
Prior art keywords
aryl
unsaturated
group
composition
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP01994423A
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German (de)
English (en)
Inventor
Paul G. c/o Honeywell International Inc. APEN
Brian c/o Honeywell International BEDWELL
Nancy c/o Honeywell International INC. IWAMOTO
Boris A. c/o Honeywell International INC. KOROLEV
Kreisler Lau
Bo c/o Honeywell International LI
Zherebin Ruslan
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Honeywell International Inc
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Honeywell International Inc
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Publication of EP1461370A1 publication Critical patent/EP1461370A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • 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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present invention relates to semiconductor devices, and in particular, to semiconductor devices having an organic low dielectric constant material and processes for the manufacture thereof.
  • dielectric constant also referred to as " ”
  • Insulator materials having low dielectric constants are especially desirable, because they typically allow faster signal propagation, reduce capacitance and cross talk between conductor lines, and lower voltages required to drive integrated circuits.
  • interconnect linewidths decrease, concomitant decreases in the dielectric constant of the insulating material are required to achieve the improved performance and speed desired of future semiconductor devices.
  • devices having interconnect linewidths of 0. 13 or 0.10 micron and below seek an insulating material having a dielectric constant (k) ⁇ 3.
  • SiO 2 silicon dioxide
  • FSG fluorinated silicon dioxide
  • FSG fluorinated silicon glass
  • SOD spin-on deposition
  • CVD chemical vapor deposition
  • Reichert and Mathias describe compounds and monomers that comprise adamantane molecules, which are in the class of cage-based molecules and are taught to be useful as diamond substitutes.
  • Polym, Prepr. Am. Chem. Soc, Div. Polym. Chem.
  • 1993, Vol. 34 (1 ), pp. 495-6 Polym, Prepr. (Am. Chem. Soc, Div. Polym. Chem.), 1992, Vol. 33 (2), pp. 144-5; Chem. Mater., 1993, Vol. 5 (1 ), pp. 4-5; Macromolecules, 1994, Vol. 27 (24), pp. 7030-7034; Macromolecules, 1994, Vol. 27 (24), pp.
  • adamantane-based compounds and monomers described by Reichert and Mathias are preferably used to form polymers with adamantane molecules at the core of a thermoset.
  • composition comprising an isomeric thermosetting monomer or dimer mixture, wherein the mixture comprises at least one monomer or dimer having the structure
  • thermosetting mixtures wherein Y is selected from cage compound and silicon atom; R 1 f R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from aryl, branched aryl, and arylene ether; at least one of the aryl, the branched aryl, and the arylene ether has an ethynyl group; and R 7 is aryl or substituted aryl.
  • This novel isomeric thermosetting monomer or dimer mixture is useful as a dielectric material in microelectronics applications and soluble in many solvents such as cyclohexanone. These desirable properties make this isomeric thermosetting monomer or dimer mixture ideal for film formation at thicknesses of about 0.1 ⁇ m to about 1 .0 ⁇ m.
  • thermosetting component wherein the thermosetting component comprises monomer having the structure
  • R 1 ( R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from aryl, branched aryl, and arylene ether; at least one of the aryl, the branched aryl, and the arylene ether has an ethynyl group; R 7 is aryl or substituted aryl; and at least one of the R 1 f R 2 , R 3 , R 4 , R 5 , and R 6 comprises at least two isomers; and (b) adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the thermosetting component (a) and the second functionality is capable of interacting with a substrate when the composition is applied to the substrate.
  • the adhesion promoter is selected from the group consisting of:
  • R 8 , R 14 , and R 17 each independently represents substituted or unsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene;
  • R 9 , R 10 , R 11 r R 12 , R 15 , and R 16 each independently represents hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene and may be linear or branched;
  • R 13 represents organosilicon, silanyl, siloxyl, or organo group; and a, b, c, and d satisfy the conditions of [4_ ⁇ a + b + c + d ⁇ 100,000], and b and c and d may collectively or independently be zero;
  • R 22 is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl
  • R 23 is alkyl, alkylene, vinylene, cycloalkylene, allylene, or aryl
  • j 3-100
  • esters of unsaturated carboxylic acids containing at least one carboxylic acid group (v) esters of unsaturated carboxylic acids containing at least one carboxylic acid group
  • a layer of composition comprising:
  • thermosetting component wherein the thermosetting component comprises monomer having the structure
  • R 1 f R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from aryl, branched aryl, and arylene ether; at least one of the aryl, the branched aryl, and the arylene ether has an ethynyl group; R 7 is aryl or substituted aryl; and at least one of R 1 f R 2 , R 3 , R 4 , R 5 , and R 6 comprises at least two isomers; and
  • adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the thermosetting component (a) and the second functionality is capable of interacting with a substrate.
  • thermosetting monomer having the structure
  • Ar is aryl
  • R , R' 2 , R' 3 , R' 4 , R' 5 , and R' 6 are independently selected from aryl, branched aryl, arylene ether, and no substitution; and wherein each of the aryl, the branched aryl, and the arylene ether has at least one ethynyl group; and (b) adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the thermosetting monomer (a) and the second functionality is capable of interacting with a substrate when the composition is applied to the substrate.
  • the adhesion promoter (b) is selected from the (i) polycarbosilanes, (ii) silanes, (iii) phenol- formaldehyde resins or oligomers, (iv) glycidyl ethers, (v) unsaturated carboxylic acid esters, or (vi) vinyl cyclic oligomers or polymers set forth above.
  • thermosetting component wherein the thermosetting component comprises monomer having the structure
  • R 1 f R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from aryl, branched aryl, and arylene ether; at least one of the aryl, the branched aryl, and the arylene ether has an ethynyl group; R 7 is aryl or substituted aryl; and at least one of the R 1 f R 2 , R 3 , R 4 , R 5 , and R 6 comprises at least two isomers; and (b) adhesion promoter comprising compound having at least-bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the thermosetting component (a) and the second functionality is capable of interacting with a substrate when the composition is applied to the substrate; and
  • the adhesion promoter (b) is selected from the (I) polycarbosilanes, (ii) silanes, (iii) phenol-formaldehyde resins or oligomers, (iv) glycidyl ethers, (v) unsaturated carboxylic acid esters, or (vi) vinyl cyclic oligomers or polymers set forth above.
  • thermosetting component (a) thermosetting component wherein the thermosetting component comprises monomer having the structure
  • R 1 f R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from aryl, branched aryl, and arylene ether; at least one of the aryl, the branched aryl, and the arylene ether has an ethynyl group; R 7 is aryl or substituted aryl; and at least one of the R 1 # R 2 , R 3 , R 4 , R 5 , and R 6 comprises at least two isomers; and (b) adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the thermosetting component (a) and the second functionality is capable of interacting with a substrate when the composition is applied to the substrate; and
  • the adhesion promoter (b) is selected from the (i) polycarbosilanes, (ii) silanes, (iii) phenol-formaldehyde resins or oligomers, (iv) glycidyl ethers, (v) unsaturated carboxylic acid esters, or (vi) vinyl cyclic oligomers or polymers set forth above.
  • spin-on low dielectric constant material comprising: (a) first backbone having first aromatic moiety and first reactive group and second backbone having second aromatic moiety and second reactive group wherein the first and second backbones are crosslinked via the first and second reactive groups in a crosslinking reaction and cage structure covalently bound to at least one of the first and second backbones, wherein the cage structure comprises at least eight atoms; and (b) adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the first and second backbones and the second functionality is capable of interacting with a substrate when the material is applied to the substrate.
  • the adhesion promoter (b) is selected from the (I) polycarbosilanes, (ii) silanes, (iii) phenol-formaldehyde resins or oligomers, (iv) glycidyl ethers, (v) unsaturated carboxylic acid esters, or (vi) vinyl cyclic oligomers or polymers set forth above.
  • Table 1 shows some of the representative teachings on low dielectric materials.
  • FIGS 1 A-1 C are contemplated structures for thermosetting monomers.
  • FIGS 1 D-1 E are contemplated structures for thermosetting dimers.
  • Figures 2A-2D are exemplary structures for thermosetting monomers comprising sexiphenylene.
  • FIGS 3A-3C are contemplated synthetic schemes for thermosetting monomers.
  • Figure 4 is a synthetic scheme to produce substituted adamantanes.
  • Figure 5 is a synthetic scheme to produce a low molecular weight polymer with pendent cage structures.
  • Figure 6 is a synthetic scheme to produce a low molecular weight polymer with pendent cage structures.
  • Figures 7 shows a synthetic scheme to produce thermosetting monomers.
  • Figures 8A-B are structures of various contemplated polymers.
  • Figures 9A-B are synthetic schemes to produce an end-capping molecule with pendent cage structures.
  • Figure 10 is schematic structure of a contemplated low dielectric constant material.
  • Figure 1 1 is a synthetic scheme for the preparation of thermosetting component comprising at least two isomers.
  • Figure 1 2 is a synthetic scheme for the preparation of the Reichert 1 ,3,5,7-tetrakis[4'-(phenylethynyl)phenyl]adamantane (para-isomer).
  • the term "at least two isomers” means at least two different isomers selected from meta, para, and ortho isomers. Preferably, the at least two isomers are meta and para isomers.
  • low dielectric constant polymer refers to an organic, organometallic, or inorganic polymer with a dielectric constant of approximately 3.0, or lower.
  • the low dielectric material is typically manufactured in the form of a thin layer having a thickness from 100 to 25,000 Angstroms but also may be used as thick films, blocks, cylinders, spheres etc.
  • backbone refers to a contiguous chain of atoms or moieties forming a polymeric strand that are covalently bound such that removal of any of the atoms or moiety would result in interruption of the chain.
  • the term "reactive group” refers to any atom, functionality, or group having sufficient reactivity to form at least one covalent bond with another reactive group in a chemical reaction.
  • the chemical reaction may take place between two identical, or non-identical reactive groups, which may be located on the same or on two separate backbones. It is also contemplated that the reactive groups may react with one or more than one secondary or exogenous crosslinking molecules to crosslink the first and second backbones.
  • crosslinking without exogenous crosslinkers presents various advantages, including reducing the overall number of reactive groups in the polymer, and reducing the number of required reaction steps, crosslinking without exogenous crosslinkers also has a few detriments. For example, the amount of crosslinking functionalities cannot typically be adjusted.
  • employing exogenous crosslinkers may be advantageous when the polymerization reaction and crosslinking reaction are chemically incompatible.
  • a cage structure, cage molecule, or cage compound comprises a plurality of rings formed by covalently bound atoms, wherein the structure, molecule, or compound defines a volume, such that a point located within the volume cannot leave the volume without passing through the ring.
  • the bridge and/or the ring system may comprise one or more heteroatoms, and may contain aromatic groups, partially cyclic or acyclic saturated hydrocarbon groups, or cyclic or acyclic unsaturated hydrocarbon groups.
  • Further contemplated cage structures include fullerenes, and crown ethers having at least one bridge.
  • an adamantane or diamantane is considered a cage structure, while a naphthalene or an aromatic spirocompound are not considered a cage structure under the scope of this definition, because a naphthalene or an aromatic spirocompound do not have one, or more than one bridge and thus, do not fall within the description of the cage compound above.
  • thermosetting component (a) or polymer means any component that when added to thermosetting component (a) or polymer, improves the adhesion thereof to substrates compared with thermosetting component (a) alone or polymer alone.
  • compound having at least bifunctionality means any compound having at least two functional groups capable of interacting or reacting, or forming bonds as follows.
  • the functional groups may react in numerous ways including addition reactions, nucleophilic and electrophilic substitutions or eliminations, radical reactions, etc. Further alternative reactions may also include the formation of non- covalent bonds, such as Van der Waals, electrostatic bonds, ionic bonds, and hydrogen bonds.
  • layer as used herein includes film and coating.
  • Thermosetting component (a) and polymer are disclosed in commonly assigned pending US Serial No. 09/618945 filed July 19, 2000; US Serial No. 09/897936 filed July 5, 2001 ; PCT/US01 /22204 filed October 1 7, 2001 ; US Serial No. 09/545058 filed April 7, 2000; and US Serial No. 09/902924 filed July 10, 2001 , which are all incorporated herein by reference.
  • Thermosetting component (a) comprises monomer having a general structure shown in Structure 1 A
  • R l f R 2 , R 3 , R 4 R 5 , and R 6 are independently selected from aryl, branched aryl, and arylene ether; and at least one of the aryl, the branched aryl, and the arylene ether has an ethynyl group.
  • R 7 is aryl or substituted aryl wherein the substituent is alkyl, halogen, or aryl.
  • aryl without further specification means aryl of any type, which may include, for example branched aryl or arylene ether.
  • Y is adamantane or diamantane.
  • Exemplary structures of thermosetting monomers that include adamantane, diamantane, and silicon atom are shown in Figures 1 A, 1 B, and 1 C, respectively, wherein n is an integer between zero and five, or more.
  • Exemplary structures of thermosetting dimers that include adamantane and diamantane are shown in Figures 1 D and 1 E respectively, wherein n is an integer between zero and five, or more.
  • thermosetting component (a) a mixture of the monomer and dimer is present.
  • the mixture comprises about 95-97 weight percent monomer and about 3-5 weight percent dimer.
  • thermosetting monomer (a) has a general structure as shown in Structure 2:
  • Ar is aryl
  • R'rR' e are independently selected from aryl, branched aryl, arylene ether, and no substitution, and wherein each of the aryl, the branched aryl, and the arylene ether has at least one ethynyl group.
  • Exemplary structures of thermosetting monomers that include a tetra-, and a hexasubstituted sexiphenylene are shown in Figures 2A-2B and 2C-2D, respectively.
  • Thermosetting monomers may be provided by various synthetic routes, and exemplary synthetic strategies for Structures 1 A and 1 B and 2 are shown in Figures 3A-3C.
  • Figure 3A depicts and Example 5 describes a preferred synthetic route for the generation of contemplated thermosetting monomers with adamantane as cage compound, in which a bromoarene is phenylethynylated in a palladium catalyzed Heck reaction.
  • adamantane (1) is brominated to 1 ,3,5,7- tetrabromoadamantane (TBA) (2) following a procedure previously described (J. Org. Chem.
  • TBA is reacted with phenyl bromide to yield 1 ,3, 5,7-tetra(374'- bromophenyDadamantane (TBPA) (3) as described in Macromolecules, 27, 701 5-7022 (1990) by Reichert, V. R, and Mathias L. J., and TBPA is subsequently reacted with a substituted ethynylaryl in a palladium catalyzed Heck reaction following standard reaction procedures to yield 1 ,3,5,7-tetrakis[3/4- (arylethynyl)phenyljadamantane (4).
  • TBPA bromophenyDadamantane
  • Example 5 goes on to show the differences between the Reichert work and compound described in the Background Section and the contemplated thermosetting component (a).
  • the palladium-catalyzed Heck reaction may also be utilized for the synthesis of a thermosetting monomer with a sexiphenylene as the aromatic portion as shown in Figures 2A-2D, in which a tetrabromosexiphenylene and a hexabromosexiphenylene, respectively, is reacted with an ethynylaryl compound to yield the desired corresponding thermosetting monomer.
  • TBA can be converted to a hydroxyarylated adamantane, which is subsequently transformed into a thermosetting monomer in a nucleophilic aromatic substitution reaction.
  • TBA (2) is generated from adamantane (1) as previously described, and further reacted in an electrophilic tetrasubstitution with phenol to yield 1 ,3,5,7-tetrakis(3'/4'- hydroxyphenyDadamantane (THPA) (5).
  • THPA hydroxyphenyDadamantane
  • TBA can also be reacted with anisole to give 1 ,3,5,7-tetrakis(374'-methoxyphenyl)adamantane (6), which can further be reacted with BBr 3 to yield THPA (5).
  • standard procedures e.g., Engineering Plastics - A Handbook of Polyarylethers by R. J. Cotter, Gordon and Breach Publishers, ISBN 2-88449-1 1 2-0
  • 4-halo-4'- fluorotolane with
  • thermosetting monomers various alternative reactants may also be utilized to generate the thermosetting monomers.
  • nucleophilic aromatic substitution reaction may also be utilized in a synthesis of a thermosetting monomer with a sexiphenylene as the aromatic portion, in which sexiphenylene is reacted with 4-fluorotolane to produce a thermosetting monomer.
  • phloroglucinol may be reacted in a standard aromatic substitution reaction with 4-[4'-(fluorophenylethynyl)phenylethynyl]benzene to yield 1 ,3,5-tris ⁇ 4'-[4"- (phenylethynyl)phenylethynyl]phenoxy ⁇ benzene.
  • cage compound is a silicon atom
  • an exemplary preferred synthetic scheme is depicted in Figure 3C, in which bromo(phenylethynyl)aromatic arms (8) where n is an integer between zero and five or more are converted into the corresponding (phenylethynyl)aryl lithium arms (9), which are subsequently reacted with silicon tetrachloride to yield the desired star-shaped thermosetting monomer with a silicon atom as a cage compound (10).
  • the cage compound is a silicon atom, an adamantane, a diamantane, or a plurality of adamantanes or diamantanes.
  • various cage compounds other than an adamantane or diamantane are also contemplated. It should be especially appreciated that the molecular size and configuration of the cage compound in combination with the overall length of the arms RrR 6 or R'rR' 6 will determine several of the physical and mechanical properties, in the final low dielectric constant polymer (by steric effect).
  • Contemplated cage compounds need not necessarily be limited to being comprised solely of carbon atoms, but may also include heteroatoms such as N, S, O, P, etc. Heteroatoms may advantageously introduce non-tetragonal bond angle configurations, which may in turn enable covalent attachment of arms RrR 6 or RyR' 6 at additional bond angles.
  • substituents and derivatizations of contemplated cage compounds it should be recognized that many substituents and derivatizations are appropriate.
  • hydrophilic substituents may be introduced to increase solubility in hydrophilic solvents, or vice versa. So, in cases where polarity is desired, polar side groups may be added to the cage compound.
  • appropriate substituents may also include thermolabile groups and nucleophilic and electrophilic groups.
  • functional groups may be utilized in the cage compound (e.g., to facilitate crosslinking reactions, derivatization reactions, etc.).
  • derivatizations include halogenation of the cage compound, and particularly preferred halogens are fluorine and bromine.
  • thermosetting monomer (a) has an aryl coupled to the arms R R' ⁇ as shown in Structure 2, it is preferred that the aryl comprises a phenyl group, and it is even more preferred that the aryl is a phenyl group to form a sexiphenylene.
  • various aryl compounds other than a phenyl group (or a sexiphenylene) are also appropriate, including substituted and unsubstituted bi- and polycyclic aromatic compounds. Substituted and unsubstituted bi- and polycyclic aromatic compounds are particularly advantageous where increased size of the thermosetting monomer is preferred.
  • aryls extend in one dimension more than in another dimension
  • naphthalene, phenanthrene, and anthracene are particularly contemplated.
  • polycyclic aryls such as a coronene are contemplated.
  • contemplated bi- and polycyclic aryls have conjugated aromatic systems that may or may not include heteroatoms.
  • substitutions and derivatizations of contemplated aryls the same considerations apply as for cage compounds, as discussed herein.
  • RrR 6 are individually selected from an aryl, a branched aryl, and an arylene ether
  • RyR'e are individually selected from an aryl, a branched aryl, and an arylene ether, and no substitution.
  • Particularly contemplated aryls for R R 6 and R'rR' 6 include aryls having a (phenylethynyl)phenyl, a phenylethynyl(phenylethynyl)phenyl, and a (phenylethynyl)phenylphenyl moiety.
  • arylene ethers include (phenylethynylphenyl)phenyl ether.
  • Particularly contemplated aryls for R 7 include phenyl and substituted aryls such as phenyl substituted with hydrogen, alkyl, aryl, or halogen.
  • appropriate arms of the thermosetting components need not be limited to an aryl, a branched aryl, and an arylene ether, so long as alternative arms R,-R 6 and R' ⁇ -R' 6 comprise a reactive group, and so long as the polymerization of the thermosetting component comprises a reaction involving the reactive group.
  • contemplated arms may be relatively short with no more than six atoms, which may or may not be carbon atoms. Such short arms may be especially advantageous where voids or pores are desirable to add to the final product or material and the size of voids needs to be relatively small.
  • the arms may comprise an oligomer or polymer with 7-40, and more atoms.
  • a cage compound may have two relatively short arms and two relatively long arms to promote dimensional growth in a particular direction during polymerization.
  • a cage compound may have two arms chemically distinct from another two arms to promote regioselective derivatization reactions.
  • a cage compound may have four arms, and only three or two of the arms carry a reactive group.
  • an aryl in a thermosetting component may have three arms wherein only two or one arm has a reactive group. It is generally contemplated that the number of reactive groups in each of the arms R -R 6 and R ⁇ -R'e may vary considerably, depending on the chemical nature of the arms and of the qualities of the desired end product. Moreover, reactive groups are contemplated to be positioned in any part of the arm, including the backbone, side chain or terminus of an arm.
  • thermosetting component (a) may be utilized as a tool to control the degree of crosslinking.
  • contemplated thermosetting monomers may have only one or two reactive groups, which may or may not be located in one arm.
  • three or more reactive groups may be included into the monomer.
  • Preferred reactive groups include electrophilic and nucleophilic groups, more preferably groups that may participate in a cycloaddition reaction and a particularly preferred reactive group is an ethynyl group.
  • thermosetting component (a) may be polymerized by a large variety of mechanisms, and the actual mechanism of polymerization predominantly depends on the reactive group that participates in the polymerization process.
  • contemplated mechanisms include nucleophilic, electrophilic and aromatic substitutions, additions, eliminations, radical polymerization reactions, and cycloaddition reaction
  • a particularly preferred polymerization mechanism is a cycloaddition that involves at least one ethynyl group located at least one of the arms.
  • the polymerization of the thermosetting component (a) may comprise a cycloaddition reaction (i.e.
  • the polymerization process may comprise a cycloaddition reaction (i.e. a chemical reaction) of the ethynyl groups.
  • cycloaddition reaction e.g., a Diels-Alder reaction
  • thermosetting component (a) takes place without participation of an additional molecule (e.g., a crosslinker), preferably as a cycloaddition reaction between reactive groups of thermosetting monomers (a).
  • additional molecule e.g., a crosslinker
  • crosslinkers may be utilized to covalently couple thermosetting component (a) to a polymer. Such covalent coupling may thereby either occur between a reactive group and a polymer or a functional group and a polymer.
  • reaction conditions may vary considerably. For example, where a monomer is polymerized by a cycloaddition reaction utilizing an ethynyl group of at least one of the arms, heating of the thermosetting monomer to approximately 250°C or greater for about 45 minutes is generally sufficient. In contrast, where the monomer is polymerized by a radical reaction, addition of a radical starter may be appropriate. Preferred polymerization methods and techniques are set forth in the examples.
  • thermosetting component may be located at any point in or on the polymer backbone, including the terminus or as a side chain of the polymer.
  • Contemplated polymers include a large variety of polymer types such as polyimides, polystyrenes, polyamides, etc. However, it is especially contemplated that the polymer comprises a polyarylene, more preferably a poly(arylene ether). In an even more preferred aspect, the polymer is fabricated at least in part from the thermosetting monomer, and it is particularly contemplated that the polymer is entirely fabricated from isomers of the thermosetting component.
  • phenylacetylene is a starting molecule that is reacted (1 ) with TBPA (supra) to yield 1 ,3,5,7-tetrakis[374'-(phenylethynyl)phenyl]adamantane (TPEPA).
  • phenylacetylene can be converted (2) to 4-
  • TBPA can then be reacted (4) with 4-(phenylethynyl)phenylacetylene to yield
  • the present invention also provides a spin-on low dielectric constant polymer comprising:
  • adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the polymer having pendant cage structures and the second functionality is capable of interacting with a substrate when the composition is applied to the substrate.
  • the adhesion promoter (b) is selected from the (i) polycarbosilanes, (ii) silanes, (iii) phenol-formaldehyde resins or oligomers, (iv) glycidyl ethers, (v) unsaturated carboxylic acid esters, or (vi) vinyl cyclic oligomers or polymers set forth above.
  • the present invention also provides a spin-on low dielectric constant material, comprising: (a) first backbone having a first aromatic moiety and a first reactive group; second backbone having a second aromatic moiety and a second reactive group, wherein the first and second backbones are crosslinked via the first and second reactive groups in a cross- linking reaction; and a cage structure covalently bound to at least one of the first and second backbones, wherein the cage structure comprises at least eight atoms; and (b) adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the first and second backbones and the second functionality is capable of interacting with a substrate when the composition is applied to the substrate.
  • At least one backbone may comprise a poly(arylene ether) with two pendent adamantane groups, respectively, as cage structures as shown in Structures 3A-B (only one repeating unit of the backbone is shown).
  • Preferred crosslinking conditions are heating the poly(arylene ether) backbones to a temperature of about 200°C-250°C or greater for approximately 30-1 80 minutes.
  • Structure 3B may be synthesized as generally outlined in Examples 1 -3 below.
  • the first and second aromatic moieties comprise a phenyl group, and the first and second reactive groups are an ethynyl, a tetracyclone, or both an ethynyl and a tetracyclone moiety, respectively, which react in a Diels-Alder reaction to cross-link the backbones.
  • the backbone need not be restricted to a poly(arylene ether), but may vary greatly depending on the desired physico- chemical properties of the final low dielectric constant material. Consequently, when relatively high T g is desired, inorganic materials are especially contemplated, including inorganic polymers comprising silicate (SiO 2 ) and/or aluminate (AI 2 O 3 ). In cases where flexibility, ease of processing, or low stress/TCE, etc. is required, organic polymers are contemplated. Thus, depending on a particular application, contemplated organic backbones include aromatic polyimides, polyamides, and polyesters.
  • the chain length of the first and second polymeric backbones may vary considerably between five, or less repeating units, to several 10 4 repeating units, and more.
  • Preferred backbones are synthesized from monomers in an aromatic substitution reaction, and synthetic routes are shown by way of example in Figures 5 and 6. It is further contemplated that alternative backbones may also be branched, superbranched, or crosslinked at least in part. Alternatively, the backbones may also be synthesized in-situ from monomers. Appropriate monomers may preferably include aromatic bisphenolic compounds and difluoroaromatic compounds, which may have between 0 and about 20 built-in cage structures.
  • thermosetting components (a) may have or comprise a tetrahedral structure, which are schematically depicted in Structures 1 A and 1 B or 4A and 4B.
  • a thermosetting monomer has a cage structure Y, and at least two of the side chains R,-R 6 comprise an aromatic portion and a reactive group, wherein at least one of the reactive groups of a first monomer reacts with at least one of the reactive group of a second monomer to produce a low dielectric constant polymer.
  • a cage structure preferably an adamantane, is coupled to four aromatic portions which may participate in polymerization, and wherein R r R 4 may be identical or different.
  • At least one of R 1 r R 2 , R 3 , and R 4 comprises at least two isomers.
  • each cage structure preferably an adamantane is coupled to three aromatic portions which may participate in polymerization and wherein R,-R e may be identical or different and two of these cage structures are joined by an aryl or substituted aryl.
  • At least one of R 1 f R 2 , R 3 , R 4 , R 6 , and R 6 comprises at least two isomers.
  • at least two isomers of the adamantanes relative to R 7 exist.
  • the cage structure When monomers with tetrahedral structure are used, the cage structure will covalently connect four backbones in a three dimensional configuration.
  • An exemplary monomer with tetrahedral structure and its synthesis is shown in Figure 3A.
  • alternative monomers need not be limited to compounds with a substituted or unsubstituted adamantane as a cage structure, but may also comprise any cycloalkyl or cycloalkylene structure, cubane, a substituted or unsubstituted diamantane, or fullerene as a cage structure.
  • Contemplated substituents include alkyls, aryls, halogens, and functional groups.
  • an adamantane may be substituted with a -CF3 group, tertiary alkyl group having from one to ten carbon atoms, a phenyl group, -COOH, -NO 2 , or -F, -CI, or -Br. Consequently, depending on the chemical nature of the cage structure, various numbers other than four aromatic portions may be attached to the cage structure. For example, where a relatively low degree of crosslinking through cage structures is desired, one to three aromatic portions may be attached to the cage structure, wherein the aromatic portions may or may not comprise a reactive group for crosslinking.
  • aromatic portions attached to a central cage structure may carry other cage structures, wherein the cage structures may be identical to the central cage structure, or may be entirely different.
  • contemplated monomers may have a fullerene cage structure to provide a relatively high number of aromatic portions, and a diamantane in the aromatic portions.
  • contemplated cage structures may be covalently bound to a first and second backbone, or to more than two backbones.
  • aromatic portions comprise a phenyl group, and more preferably a phenyl group and a reactive group.
  • an aromatic portion may comprise a tolane or (phenylethynylphenyl) group, or a substituted tolane, wherein substituted tolanes may comprise additional phenyl groups covalently bound to the tolane via carbon-carbon bonds, or carbon-non-carbon atom bonds, including double and ethynyl groups, ether-, keto-, or ester groups.
  • pending cage structures are not limited to two diamantane structures.
  • Contemplated alternative cage structures include single and multiple substituted adamantane groups, diamantane groups and fullerenes in any chemically reasonable combination. Substitutions may be introduced into the cage structures in cases where a particular solubility, oxidative stability, or other physico- chemical properties are desired. Therefore, contemplated substitutions include halogens, alkyl, aryl, and alkenyl groups, but also functional and polar groups including esters, acid groups, nitro and amino groups, and so forth.
  • backbones need not be identical.
  • two, or more than two chemically distinct backbones may be utilized to fabricate a low dielectric constant material, as long as the alternative low dielectric constant material comprises first and second backbones having an aromatic moiety, a reactive group, and a cage compound covalently bound to the backbone.
  • reactive groups it is contemplated that many reactive groups other than an ethynyl group and a tetracyclone group may be utilized, so long as alternative reactive groups are able to crosslink first and second backbones without an exogenous crosslinker.
  • appropriate reactive groups include benzocyclobutenyl.
  • a first reactive group may comprise an electrophile, while a second reactive group may comprise a nucleophile. It is further contemplated that the number of reactive groups predominantly depends on (a) the reactivity of the first and second reactive group, (b) the strength of the crosslink between first and second backbone, and (c) the desired degree of crosslinking in the low dielectric material.
  • first and second reactive groups are sterically hindered (e.g. an ethynyl group between two derivatized phenyl rings)
  • a relatively high number of reactive groups may be needed to crosslink two backbones to a certain extent.
  • a high number of reactive groups may be required to achieve stable crosslinking when relatively weak bonds such as hydrogen bonds or ionic bonds are formed between the reactive groups.
  • a reactive group in one backbone is capable of reacting with an identical reactive group in another backbone
  • only one type of reactive group may be needed.
  • ethynyl groups located on the same of two different backbones may react in an addition and cycloaddition-type reaction to form crosslinking structures.
  • the number of reactive groups may influence the ratio of intermolecular to intramolecular crosslinking. For example, a relatively high concentration of reactive groups in first and second backbones at a relatively low concentration of both backbones may favor intramolecular reactions. Similarly, a relatively low concentration of reactive groups in first and second backbones at a relatively high concentration of both backbones may favor intermolecular reactions.
  • the balance between intra- and intermolecular reactions may also be influenced by the distribution of non- identical reactive groups between the backbones. When an intermolecular reaction is desired, one type of reactive group may be placed on the first backbone, while another type of reactive group may be positioned on the second backbone.
  • additional third and fourth reactive groups may be utilized when sequential crosslinking at different conditions is desired (e.g. two different temperatures).
  • the reactive groups of preferred backbones react in an addition-type reaction, however, depending on the chemical nature of alternative reactive groups, many other reactions are also contemplated, including nucleophilic and electrophilic substitutions, or eliminations, radical reactions, etc. Further alternative reactions may also include the formation of non-covalent bonds, such as electrostatic bonds, ionic bonds, and hydrogen bonds.
  • crosslinking the first and second backbone may occur via a covalent or non- covalent bond formed between identical or non-identical reactive groups, which may be located on the same or two backbones.
  • the cage structure may comprise structures other than an adamantane, including a diamantane, bridged crown ethers, cubanes, or fullerenes, as long as alternative cage structures have at least eight atoms.
  • the selection of appropriate cage structures is determined by the desired degree of steric demand of the cage structure. If relatively small cage structures are preferred, a single adamantane, or diamantane group may be sufficient. Contemplated structures of backbones including adamantane and diamantane groups are shown in Figures 8A and 8B. Large cage structures may comprise fullerenes. It should also be appreciated that alternative backbones need not be limited to a single type of cage structure.
  • Appropriate backbones may also include two to five cage structures or other molecules and more non-identical cage structures. For example, fullerenes may be added to one or both ends of a polymeric backbone, while diamantane groups are placed in the other parts of the backbone. Further contemplated are derivatized, or multiple cage structures, including oligo- merized and polymerized cage structures, where even larger cage structures are desired.
  • the chemical composition of the cage structures need not be limited to carbon atoms, and it should be appreciated that alternative cage structures may have atoms other than carbon atoms (i.e. heteroatoms), whereby contemplated heteroatoms may include N, O, P, S, B, etc.
  • the cage structure may be connected to the backbone in various locations.
  • the cage structure may be utilized as an end-cap.
  • Exemplary structures of end- caps are shown in Figures 9A and 9B.
  • the cage structures are pendent structures covalently connected to the backbone.
  • the position of the covalent connection may vary, and mainly depends on the chemical make-up of the backbone and the cage structure. Thus, appropriate covalent connections may involve a linker molecule, or a functional group, while other connections may be a single or double bond.
  • the cage group is a pendent group
  • more than one backbone may be connected to the cage structure.
  • a single cage structure may connect at least two or three or and more backbones.
  • the cage group may be an integral part of the backbone.
  • a first backbone 10 is crosslinked to a second backbone 20 via a first reactive group G 1 5 and a second reactive group G25, wherein the crosslinking results in a covalent bond 50.
  • Both backbones have at least one aromatic moiety (not shown), respectively.
  • a plurality of pendent cage structures 30 are covalently bound to the first and second backbones, and the first backbone 10 further has a terminal cage group 32.
  • the terminal cage group 32, and at least one of the pendent cage groups 30 carries at least one substituent R (40), wherein substituent 40 may be a halogen, alkyl, or aryl group.
  • Each of the cage structures comprises at least eight (8) atoms.
  • One adhesion promoter is silanes of the formula (R ⁇ 8 ) f (R 19 ) ⁇ Si(R 20 ) h (R 21 ) i wherein R 18r R 19 , R 20 , and R 21 each independently represents hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl where the substituent is amino or epoxy, saturated or unsaturated alkoxyl, unsaturated or saturated carboxylic acid radical, or aryl wherein at least two of R 18 , R 19 R 20 , and R 21 represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid radical; and f + g + h + i ⁇ 4.
  • Examples of useful alkyl groups include -CH 2 - and -(CH 2 ) k - where k > 1 .
  • a particularly useful phenol-formaldehyde resin oligomer has a molecular weight of 1 500 and is commercially available from Schenectady International.
  • glycidyl ethers including but not limited to 1 , 1 , 1 -tris-(hydroxyphenyl)ethane tri-glycidyl ether which is commercially available from TriQuest.
  • esters of unsaturated carboxylic acids containing at least one carboxylic acid group examples include trifunctional methacrylate ester, trifunctional acrylate ester, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and glycidyl methacrylate.
  • trifunctional methacrylate ester trifunctional acrylate ester
  • trimethylolpropane triacrylate trimethylolpropane triacrylate
  • dipentaerythritol pentaacrylate dipentaerythritol pentaacrylate
  • glycidyl methacrylate glycidyl methacrylate
  • Useful examples include but not limited to 2-vinylpyridine and 4-vinylpyridine, commercially available from Reilly; vinyl aromatics; and vinyl heteroaromatics including but not limited to vinyl quinoline, vinyl carbazole, vinyl imidazole, and vinyl , oxazole.
  • adhesion promoter (b) is the polycarbosilane disclosed in commonly assigned copending US patent application Serial 09/471299 filed December 23, 1999 incorporated herein by reference in its entirety.
  • the polycarbosilane is of the formula (I):
  • R 8 , R 14 , and R 17 each independently represents substituted or unsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene;
  • R 9 , R 10 , R 11 f R 12 , R 15 and R 16 each independently represents hydrogen atom or organo group comprising alkyl, alkylene, vinyl, cycloalkyl, allyl, or aryl and may be linear or branched;
  • R 13 represents organosilicon, silanyl, siloxyl, or organo group; and a, b, c, and d satisfy the conditions of [4 ⁇ a + b + c + d ⁇ _100,000], and b and c and d may collectively or independently be zero.
  • the organo groups may contain up to 18 carbon atoms but generally contain from about 1 to about 10 carbon atoms.
  • Useful alkyl groups include -CH 2 - and -(CH 2 ) e - where e > 1 .
  • Preferred polycarbosilanes of the present invention include dihydrido polycarbosilanes in which R 8 is a substituted or unsubstituted alkylene or phenyl, R 9 group is a hydrogen atom and there are no appendent radicals in the polycarbosilane chain; that is, b, c, and d are all zero.
  • polycarbosilanes are those in which the R 9 , R 10 , R , R 12 , R 15 , and R 16 groups of formula (I) are substituted or unsubstituted alkenyl groups having from 2 to 10 carbon atoms.
  • the alkenyl group may be ethenyl, propenyl, allyl, butenyl or any other unsaturated organic backbone radical having up to 10 carbon atoms.
  • the alkenyl group may be dienyl in nature and includes unsaturated alkenyl radicals appended or substituted on an otherwise alkyl or unsaturated organic polymer backbone.
  • polycarbosilanes examples include dihydrido or alkenyl substituted polycarbosilanes such as polydihydridocarbosilane, polyallylhydrididocarbosilane and random copolymers of polydihydridocarbosilane and polyallylhydridocarbosilane.
  • the R 9 group of formula I is a hydrogen atom and R 8 is methylene and the appendent radicals b, c, and d are zero.
  • Other preferred polycarbosilane compounds of the invention are polycarbosilanes of formula I in which R 9 and R 15 are hydrogen, R 8 and R 17 are methylene, and R 16 is an alkenyl, and appendent radicals b and c are zero.
  • the polycarbosilanes may be prepared from well known prior art processes or provided by manufacturers of polycarbosilane compositions.
  • These most preferred polycarbosilanes may be obtained from Starfire Systems, Inc. Specific examples of these most preferred polycarbosilanes follow:
  • the polycarbosilanes utilized in the subject invention may contain oxidized radicals in the form of siloxyl groups when c > 0.
  • R 13 represents organosilicon, silanyl, siloxyl, or organo group when c > 0. It is to be appreciated that the oxidized versions of the polycarbosilanes (c > 0) operate very effectively in, and are well within the purview of the present invention.
  • c can be zero independently of a, b, and d the only conditions being that the radicals a, b, c, and d of the formula I polycarbosilanes must satisfy the conditions of [4 ⁇ a + b + c + d ⁇ 100,000], and b and c can collectively or independently be zero.
  • the present polycarbosilanes are preferably added in small, effective amounts from about 0.5% to up to 20% based on the weight of the present thermosetting composition (a) and amounts up to about 5.0 % by weight of the composition are generally more preferred.
  • the polycarbosilane may be produced from starting materials that are presently commercially available from many manufacturers and by using conventional polymerization processes.
  • the starting materials may be produced from common organo silane compounds or from polysilane as a starting material by heating an admixture of polysilane with polyborosiloxane in an inert atmosphere to thereby produce the corresponding polymer or by heating an admixture of polysilane with a low molecular weight carbosilane in an inert atmosphere to thereby produce the corresponding polymer or by heating an admixture of polysilane with a low molecular carbosilane in an inert atmosphere and in the presence of a catalyst such as polyborodiphenylsiloxane to thereby produce the corresponding polymer.
  • Polycarbosilanes may also be synthesized by Grignard Reaction reported in U.S. Patent 5, 1 53,295 hereby incorporated by reference.
  • the resulting compositions have superior adhesion characteristics throughout the entire polymer so as to ensure affinity to any contacted surface of the coating.
  • Present polycarbosilane also improves striation control, viscosity, and film uniformity. Visual inspection confirms the presence of improved striation control.
  • compositions may also comprise additional components such as additional adhesion promoters, antifoam agents, detergents, flame retardants, pigments, plasticizers, stabilizers, and surfactants.
  • additional adhesion promoters such as additional adhesion promoters, antifoam agents, detergents, flame retardants, pigments, plasticizers, stabilizers, and surfactants.
  • thermosetting component (a) and adhesion promoter (b) may be combined with other specific additives to obtain specific results.
  • additives include metal-containing compounds such as magnetic particles, for example, barium ferrite, iron oxide, optionally in a mixture with cobalt, or other metal containing particles for use in magnetic media, optical media, or other recording media; conductive particles such as metal or carbon for use as conductive sealants; conductive adhesives; conductive coatings; electromagnetic interference (EMI)/radio frequency interference (RFI) shielding coating; static dissipation; and electrical contacts.
  • the present compositions may act as a binder.
  • the present compositions may also be employed as protection against manufacturing, storage, or use environment such as coatings to impart surface passivation to metals, semiconductors, capacitors, inductors, conductors, solar cells, glass and glass fibers, quartz, and quartz fibers.
  • thermosetting component (a) and adhesion promoter (b) are also useful in seals and gaskets, preferably as a layer of a seal or gasket, for example around a scrim, also alone.
  • the composition is useful in anti-fouling coatings on such objects as boat parts; electrical switch enclosures; bathtubs and shower coatings; in mildew resistant coatings; or to impart flame resistance, weather resistance, or moisture resistance to an article. Because of the range of temperature resistance of the present compositions, the present compositions may be coated on cryogenic containers, autoclaves, and ovens, as well as heat exchanges and other heated or cooled surfaces and on articles exposed to microwave radiation.
  • thermosetting component (a) and adhesion promoter (b) is useful as a dielectric material.
  • the dielectric material has a dielectric constant k of less than 3.0.
  • Layers of the instant compositions of thermosetting component (a) and adhesion promoter (b) may be formed by solution techniques such as spraying, rolling, dripping, spin coating, flow coating, or casting, with spin coating being preferred for microelectronics.
  • the present composition is dissolved in a solvent.
  • Suitable solvents for use in such solutions of the present compositions include any suitable pure or mixture of organic, organometallic, or inorganic molecules that are volatized at a desired temperature.
  • Suitable solvents include aprotic solvents, for example, cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone; cyclic amides such as N-alkylpyrrolidinone wherein the alkyl has from about 1 to 4 carbon atoms; and N-cyclohexylpyrrolidinone and mixtures thereof.
  • aprotic solvents for example, cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone; cyclic amides such as N-alkylpyrrolidinone wherein the alkyl has from about 1 to 4 carbon atoms; and N-cyclohexylpyrrolidinone and mixtures thereof.
  • aprotic solvents for example, cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone
  • solvents include methyethylketone, methylisobutylketone, dibutyl ether, cyclic dimethylpolysiloxanes, butyrolactone, ⁇ -butyrolactone, 2-heptanone, ethyl 3-ethoxypropionate, polyethylene glycol methyl ether, propylene glycol methyl ether acetate, mesitylene, anisole, and hydrocarbon solvents such as xylenes, benzene, and toluene.
  • Preferred solvent is cyclohexanone.
  • layer thicknesses are between 0.1 to about 1 5 microns. As a dielectric interlayer for microelectronics, the layer thickness is generally less than 2 microns.
  • thermosetting component (a) and adhesion promoter (b) and solvent is treated at a temperature from about 30°C to about 350°C for about 0.5 to about 60 hours.
  • This treatment generally forms an oligomer of the thermosetting component (a) and adhesion promoter (b) as evidenced by GPC.
  • the present composition may be used in electrical devices and more specifically, as an interlayer dielectric in an interconnect associated with a single integrated circuit ("IC") chip.
  • An integrated circuit chip typically has on its surface a plurality of layers of the present composition and multiple layers of metal conductors. It may also include regions of the present composition between discrete metal conductors or regions of conductor in the same layer or level of an integrated circuit.
  • a solution of the present composition is applied to a semiconductor wafer using conventional wet coating processes such as, for example, spin coating; other well known coating techniques such as spray coating or flow coating may be employed in specific cases.
  • a cyclohexanone solution of the present composition is spin-coated onto a substrate having electrically conductive components fabricated therein and the coated substrate is then subjected to thermal processing.
  • An exemplary formulation of the instant composition is prepared by dissolving the present composition in cyclohexanone solvent under ambient conditions with strict adherence to a clean-handling protocol to prevent trace metal contamination in any conventional apparatus having a non- metallic lining.
  • the resulting solution comprises based on the total solution weight, from preferably about 1 to about 50 weight percent of thermosetting component (a) and adhesion promoter (b) and about 50 to about 99 weight percent solvent and more preferably from about 3 to about 20 weight percent of thermosetting component (a) and adhesion promoter (b) and about 80 to about 97 weight percent solvent.
  • compositions used herein have a controlled viscosity suitable for such a coater.
  • Evaporation of the solvent by any suitable means, such as simple air drying during spin coating, by exposure to an ambient environment, or by heating on a hot plate up to 350°C, may be employed.
  • the substrate may have at least two layers of the present composition of thermosetting component (a) and adhesion promoter (b).
  • Substrates contemplated herein may comprise any desirable substantially solid material. Particularly desirable substrate layers comprise films, glass, ceramic, plastic, metal or coated metal, or composite material.
  • the substrate comprises a silicon or gallium arsenide die or wafer surface, a packaging surface such as found in a copper, silver, nickel or gold plated leadframe, a copper surface such as found in a circuit board or package interconnect trace, a via-wall or stiffener interface ("copper” includes considerations of bare copper and its oxides), a polymer- based packaging or board interface such as found in a polyimide-based flex package, lead or other metal alloy solder ball surface, glass and polymers.
  • the substrate comprises a material common in the packaging and circuit board industries such as silicon, copper, glass, and polymers.
  • the present compositions may also be used as a dielectric substrate material in microchips, multichip modules, laminated circuit boards, or printed wiring boards.
  • the circuit board made up of the present composition will have mounted on its surface patterns for various electrical conductor circuits.
  • the circuit board may include various reinforcements, such as woven non-conducting fibers or glass cloth.
  • Such circuit boards may be single sided, as well as double sided.
  • Layers made from the present compositions possess a low dielectric constant, high thermal stability, high mechanical strength, and excellent adhesion to electronic substrate surfaces including silicon, silicon nitride, silicon oxide, silicon oxycarbide, silicon dioxide, silicon carbide, silicon oxynitride, titanium nitride, tantalum nitride, tungsten nitride, aluminum, copper, tantalum, organosiloxanes, organo silicon glass, and fluorinated silicon glass. Because the adhesion promoter is molecularly dispersed, these layers demonstrate excellent adhesion to all affixed surfaces including underlying substrates and overlaid capping or masking layers, such as Si0 2 and Si 3 N 4 capping layers. The use of these layers eliminates the need for an additional process step in the form of at least one primer coating application to achieve adhesion of the film to a substrate and/or overlaid surface.
  • the coated structure is subjected to a bake and cure thermal process at increasing temperatures ranging from about 50°C up to about 450°C to polymerize the coating.
  • the curing temperature is at least about 300°C because a lower temperature is insufficient to complete the reaction herein.
  • curing is carried out at temperatures of from about 375°C to about 425°C.
  • Curing may be carried out in a conventional curing chamber such as an electric furnace, hot plate, and the like and is generally performed in an inert (non-oxidizing) atmosphere (nitrogen) in the curing chamber.
  • Any non oxidizing or reducing atmospheres e.g., argon, helium, hydrogen, and nitrogen processing gases
  • argon, helium, hydrogen, and nitrogen processing gases may be used in the practice of the present invention, if they are effective to conduct curing of the present organosilicon-modified thermosetting component (a) or polymer to achieve the low k dielectric layer herein.
  • thermosetting component (a) While not to be construed as limiting, it is speculated that the thermal processing of the present low dielectric constant composition results in a crosslinked network of thermosetting component (a) and adhesion promoter
  • thermosetting component (a) to convert to silylene/silyl radicals which then react with both the unsaturated structures of thermosetting component (a) and the substrate surfaces, thereby creating a chemically bonded adherent interface for the dominant thermosetting monomer (a) precursor with these silylene/ silyl radicals being available throughout the composition to act as attachment sources to fasten and secure any interface surface of contact by chemical bonding therewith.
  • This reaction may also occur during formulation or treatment prior to layer formation.
  • this dispersion of radicals throughout the composition accounts for the superb adhesion of the instant layers to both underlying substrate surfaces as well as overlayered surface structures such as cap or masking layers.
  • polycarbosilanes adhesion promoters have a reactive hydrido substituted silicon in the backbone structure of the polycarbosilane.
  • This feature of the polycarbosilane enables it to: (1 ) be reactive with thermosetting component (a) and; (2) generate a polycarbosilane-modified thermosetting component (a) which possesses improved adhesion performance.
  • the resulting layer has a low dielectric constant k defined herein as being 3.0 or less.
  • the present polycarbosilane-modified thermosetting component (a) or polymer coating may act as an interlayer and be covered by other coatings, such as other dielectric (SiO 2 ) coatings, SiO 2 modified ceramic oxide layers, silicon containing coatings, silicon carbon containing coatings, silicon nitrogen containing coatings, silicon-nitrogen-carbon containing coatings, diamond like carbon coatings, titanium nitride, tantalum nitride, tungsten nitride, aluminum, copper, tantalum, organosiloxanes, organo silicon glass, and fluorinated silicon glass.
  • Such multilayer coatings are taught in U.S. Pat. No. 4,973,526, which is incorporated herein by reference.
  • the present polycarbosilane-modified thermosetting component (a) prepared in the instant process may be readily formed as interlined dielectric layers between adjacent conductor paths on fabricated electronic or semiconductor substrates.
  • the present films may be used in copper dual damascene processing or substractive metal (such as aluminum) processing for integrated circuit manufacturing.
  • the present composition may be used in a desirable all spin-on stacked film as taught by Michael E. Thomas, "Spin-On Stacked Films for Low k eff Dielectrics", Solid State Technology (July 2001 ), incorporated herein in its entirety by reference.
  • Proton NMR A 2-5 mg sample of the material to be analyzed was put into an NMR tube. About 0.7 ml deuterated chloroform was added. The mixture was shaken by hand to dissolve the material. The sample was then analyzed using a Varian 400MHz NMR.
  • HPLC High Performance Liquid Chromatography
  • the samples were prepared as follows.
  • GPC Gel Permeation Chromatography
  • the sample (10 milligrams) was prepared by adding to tetrahydrofuran (one milliliter).
  • Finnigan/MAT TSQ7000 triple stage quadrupole mass spectrometer system with an Atmospheric Pressure Ionization (API) interface unit, using a Hewlett-Packard Series 1050 HPLC system as the chromatographic inlet. Both mass spectral ion current and variable single wavelength UV data were acquired for time-intensity chromatograms. Chromatography was conducted on a Phenomenex Luna 5 micron phenyhexyl column (250x4.6mm). Sample auto-injections were generally 10 or 20 microliters of concentrated solutions, both in tetrahydrofuran and without tetrahydrofuran.
  • the mobile phase flow through the column was 1 .0 microliter/minute of acetonitrile/water, initially 70/30 for 5 minutes then programmed to 100% acetonitrile at 1 5 minutes and held until 100 minutes (longer than actually necessary to thoroughly elute material from the column).
  • Atmospheric Pressure Chemical Ionization (APCI) mass spectra were recorded alternately in both positive and negative ion modes.
  • the APCI corona discharge was 5 microA, about 5kV for positive ionization, and about 4kV for negative ionization.
  • the heated capillary line was maintained at 200°C and the vaporizer cell at 400°C.
  • the on detection system after quadrupole mass analysis was set at 1 5kV conversion dynode and 1 500 V electron multiplier voltage. Mass spectra were typically scanned at 0.5 sec/scan from about m/z 1 50 to 2000 a.m.u. for positive ionization and m/z 1 25 to 2000 a.m.u. for negative ionization modes.
  • DSC Differential Scanning Calorimetrv
  • Sample was heated under nitrogen from 0°C to 450°C at a rate of 100°C/minute (cycle 1 ), then cooled to 0°C at a rate of 100°C/minute.
  • a second cycle was run immediately from 0°C to 450°C at a rate of 100°C/minute (repeat of cycle 1 ).
  • the cross-linking temperature was determined from the first cycle.
  • FTIR analysis FTIR spectra were taken using a Nicolet Magna 550 FTIR spectrometer in transmission mode. Substrate background spectra were taken on uncoated substrates. Film spectra were taken using the substrate as background. Film spectra were then analyzed for change in peak location and intensity.
  • Dielectric Constant The dielectric constant was determined by coating a thin film of aluminum on the cured layer and then doing a capacitance- voltage measurement at 1 MHz and calculating the k value based on the layer thickness.
  • Tg Glass Transition Temperature
  • the glass transition temperature of a thin film was determined by measuring the thin film stress as a function of temperature. The thin film stress measurement was performed on a KLA 3220 Flexus. Before the film measurement, the uncoated wafer was annealed at 500°C for 60 minutes to avoid any errors due to stress relaxation in the wafer itself. The wafer was then deposited with the material to be tested and processed through all required process steps. The wafer was then placed in the stress gauge, which measured the wafer bow as function of temperature. The instrument calculated the stress versus temperature graph, provided that the wafer thickness and the film thickness were known. The result was displayed in graphic form. To determine the Tg value, a horizontal tangent line was drawn (a slope value of zero on the stress vs. temperature graph). Tg value was where the graph and the horizontal tangent line intersect. It should be reported if the Tg was determined after the first temperature cycle or a subsequent cycle where the maximum temperature was used because the measurement process itself may influence Tg.
  • Isothermal Gravimetric Analysis Weight Loss: Total weight loss was determined on the TA Instruments 2950 Thermogravimetric Analyzer (TGA) used in conjunction with a TA Instruments thermal analysis controller and associated software. A Platinel II Thermocouple and a Standard Furnace with a temperature range of 25°C to 1000°C and heating rate of 0.1 °C to 100°C/min were used. A small amount of sample (7 to 1 2 mg) was weighed on the TGA's balance (resolution: 0.1 g; accuracy: to ⁇ 0.1 %) and heated on a platinum pan.
  • TGA Thermogravimetric Analyzer
  • Samples were heated under nitrogen with a purge rate of 100 ml/min (60 ml/min going to the furnace and 40 ml/min to the balance). Sample was equilibrated under nitrogen at 20°C for 20 minutes, then temperature was raised to 200°C at a rate of 10°C/minute and held at 200°C for 10 minutes. Temperature was then ramped to 425°C at a rate of 10°C/minute and held at 425°C for 4 hours. The weight loss at 425°C for the 4 hour period was calculated.
  • Shrinkage Film shrinkage was measured by determining the film thickness before and after the process. Shrinkage was expressed in percent of the original film thickness. Shrinkage was positive if the film thickness decreased. The actual thickness measurements were performed optically using a J.A. Woollam M-88 spectroscopic ellipsometer. A Cauchy model was used to calculate the best fit for Psi and Delta (details on Ellipsometry can be found in e.g. "Spectroscopic Ellipsometry and Reflectometry" by H.G. Thompkins and William A. McGahan, John Wiley and Sons, Inc., 1 999).
  • the refractive index measurements were performed together with the thickness measurements using a J.A. Woollam M-88 spectroscopic ellipsometer. A Cauchy model was used to calculate the best fit for Psi and Delta. Unless noted otherwise, the refractive index was reported at a wavelenth of 633nm (details on Ellipsometry can be found in e.g. "Spectroscopic Ellipsometry and Reflectometry" by H.G. Thompkins and William A. McGahan, John Wiley and Sons, Inc., 1999).
  • Modulus and Hardness were measured using instrumented indentation testing. The measurements were performed using a MTS Nanoindenter XP (MTS Systems Corp., Oak Ridge, TN). Specifically, the continuous stiffness measurement method was used, which enabled the accurate and continuous determination of modulus and hardness rather than measurement of a discrete value from the unloading curves.
  • the system was calibrated using fused silica with a nominal modulus of 72 + - 3.5 GPa. The modulus for fused silica was obtained from average value between 500 to 1000 nm indentation depth. For the thin films, the modulus and hardness values were obtained from the minimum of the modulus versus depth curve, which is typically between 5 to 1 5% of the film thickness.
  • the tape test was performed following the guidelines given in ASTM D3359-95. A grid was scribed into the dielectric layer according to the following. A tape test was performed across the grid marking in the following manner: (1 ) a piece of adhesive tape, preferably Scotch brand #3m600-1 /2X1296, was placed on the present layer, and pressed down firmly to make good contact; and (2) the tape was then pulled off rapidly and evenly at an angle of 180° to the layer surface. The sample was considered to pass if the layer remained intact on the wafer, or to have failed if part or all of the film pulled up with the tape.
  • a piece of adhesive tape preferably Scotch brand #3m600-1 /2X1296, was placed on the present layer, and pressed down firmly to make good contact; and (2) the tape was then pulled off rapidly and evenly at an angle of 180° to the layer surface. The sample was considered to pass if the layer remained intact on the wafer, or to have failed if part or all of the film pulled up with the tape.
  • Epoxy-coated studs were attached to the surface of a wafer containing the layers of the present invention.
  • a ceramic backing plate was applied to the back side of the wafer to prevent substrate bending and undue stress concentration at the edges of the stud.
  • the studs were then pulled in a direction normal to the wafer surface by a testing apparatus employing standard pull protocol steps. The stress applied at the point of failure and the interface location were then recorded.
  • Compatibility with Solvents was determined by measuring film thickness, refractive index, FTIR spectra, and dielectric constant before and after solvent treatment. For a compatible solvent, no significant change should be observed.
  • resorcinol 1 1 .00g, l OO.OmMol
  • bromoadamantane 44.02 g, 205.1 mMol
  • toluene 1 50mL
  • the mixture was heated to 1 10°C and became a clear solution.
  • the reaction was allowed to continue for 48h, at which time TLC showed that all the resorcinol had disappeared.
  • the solvent was removed and the solid was crystallized from hexanes (150mL).
  • the disubstituted product was obtained in 66.8% yield (25.26g) as a white solid.
  • Another 5.10g product was obtained by silica gel column chromatography of the concentrated mother liquor after the first crop. The total yield of the product was 80.3%. Characterization of the product was by proton NMR, HPLC, FTIR, and MS.
  • a composition is formed from the product of Example 1 , silane adhesion promoter, and solvent and then spun onto a substrate.
  • Example 1 The synthetic procedure of Example 1 is followed except that 3,4- difluorotetraphenylcyclodienone is used as the difluoro compound.
  • a composition is formed from the product of Example 2, phenol- formaldehyde resin adhesion promoter, and solvent and then spun onto a substrate.
  • a composition is formed from the product of Example 2A, glycidyl ether adhesion promoter, and solvent and then spun onto a substrate.
  • Example 3
  • composition is formed from the first polymer of Example 3, unsaturated carboxylic acid ester adhesion promoter, and solvent and then spun onto a substrate.
  • composition is formed from the second polymer of Example 3, vinyl pyridine oligomer or polymer adhesion promoter, and solvent and then spun onto a substrate.
  • Example 3C The composition is formed from the third polymer of Example 3, vinyl aromatic oligomer or polymer adhesion promoter, and solvent and then spun onto a substrate.
  • composition is formed from the fourth polymer of Example 3, vinyl heteroaromatic oligomer or polymer adhesion promoter, and solvent and then spun onto a substrate.
  • a composition is formed from the product of Example 4, vinyl silane adhesion promoter, and solvent and then spun onto a substrate.
  • Example 5 A composition is formed from the product of Example 4, vinyl silane adhesion promoter, and solvent and then spun onto a substrate.
  • thermosetting component (a) This example illustrates the preparation of a thermosetting component (a).
  • Step 1 Synthesis of 1 ,3.5,7-Tetrabromoadamantane (TBA)
  • TBA was reacted with bromobenzene to yield supposedly 1 ,3,5,7-tetrakis(3/4-bromophenyl)adamantane (TBPA) as described in Macromolecules, 27, 701 5-7023 (1 994) (supra).
  • HPLC-MS analysis showed that of the total reaction product the percentage of the desired TBPA present was approximately 50%, accompanied by 40% of the tribrominated tetraphenyladamantane, and about 10% of the dibrominated tetraphenyladamantane.
  • the dark reaction mixture was poured into a 20L reactor containing 7L (21 7% v/v relative to the total volume of bromobenzene) deionized water, 2L (62% v/v relative to the total volume of bromobenzene) ice, and 300mL (37%) HCl (9% v/v relative to the total volume of bromobenzene).
  • the reaction mixture was stirred vigorously using an overhead-stirrer for 1 hr ⁇ 10min.
  • the organic layer was transferred to a separatory chamber and washed twice with 700mL (22% v/v relative to the total volume of bromobenzene) portions of de-ionized water.
  • the washed organic layer was placed in a 4L separatory funnel and added, as a slow stream, to 1 6L (5 x times to the total volume of bromobenzene) methanol, in a 30L reactor placed under an overhead-stirrer, to precipitate a solid during 25min ⁇ 5min.
  • the methanol suspension was agitated vigorously for 1 hr ⁇ 10min.
  • the methanol suspension was filtered by suction through a Buchner funnel (185mm).
  • the solid was washed on filter cake with three portions of 600mL (19% v/v relative to the total volume of bromobenzene) methanol.
  • the solid was suctioned dry for 30 min.
  • the corresponding amounts of bromobenzene and aluminum bromide needed were calculated based on the yield of the TBPA synthesized in the above/conventional synthesis.
  • the appropriate amount (80% v/v from the total volume) of bromobenzene was poured into the flask and the stir-bar was activated.
  • the full amount of TBPA from the Step 2 synthesis above was added and the funnel was rinsed with appropriate amount (10% v/v from the total volume) of bromobenzene.
  • An HPLC sample of starting material was taken and compared with standard HPLC chromatogram.
  • the full amount of aluminum bromide was added to the solution and the funnel was rinsed with remainder (10% from the total volume) of bromobenzene.
  • the organic layer was transferred to a separatory funnel and washed twice with 700mL (22% v/v to the total volume of bromobenzene) portions of deionized water and 3 times with 700mL (22% v/v relative to the total volume of bromobenzene) portions of saturated NaCI solution.
  • the washed organic layer was placed in a 4L separatory funnel and added, as a slow stream, to the appropriate amount (5 x times to the total volume of bromobenzene) methanol, in a 30L reactor placed under an overhead-stirrer, to precipitate a solid for 25min ⁇ 5min. After addition was complete, the methanol suspension was agitated vigorously for 1 hr ⁇ 10min.
  • the methanol suspension was filtered by suction through a Buchner funnel (1 85mm). The solid was washed on filter cake with three portions of 600mL (19% v/v relative to the total amount of bromobenzene) methanol. The solid was suctioned dry for 30 min.
  • the resulting pinkish powder was emptied into a crystallizer dish using a spatula, placed in an oven to dry overnight, weighed after drying, and re- dried in the vacuum-oven for 2 additional hours, until the weight change was
  • Step 4 Synthesis of Mixture of 1.3,5.7-tetrakis.374'- (phenylethvnyl)phenylladamantane (TPEPA) and 1.3/4-bis ⁇ r.3'.5 / - trisr3 , 74"-(phenylethvnyl)phenylladamantyl ⁇ benzene (BTPEPAB)
  • Step 4 the experimental procedure for this Step 4 synthesis follows.
  • the following equipment was assembled: dry 2L 3-neck round bottom flask, water condenser, overhead-stirrer, heating mantle, thermocouple, thermal controller unit, dropping funnel, 2-necked adapter, and N 2 inlet-outlet to 30% KOH solution.
  • the flask was purged with N 2 for 10 min.
  • TEA triethylamine
  • the total amount of TBPA from the Step 3 synthesis above was added and rinsed the funnel with 100mL (8% of total volume) TEA.
  • the flask was heated to 80°C. Once the reaction mixture temperature reached 80°C, a HPLC sample was taken for analysis. This was the starting material.
  • the measured quantity of phenylacetylene diluted with 50mL (4% of total volume) TEA was placed in the dropping funnel, mounted on one neck of the 2-necked adapter. The diluted phenylacetylene was added dropwise to the reaction mixture over 30min ⁇ 10min. This was an exothermic reaction.
  • the temperature was controlled by using a water bath. The heating continued for 3 hours. The reaction was stopped after 3 hours of heating at 80°C.
  • An HPLC sample was taken at time 3 hours at 80°C.
  • the reaction mixture was cooled to 50°C and then filtered through a Buchner funnel. (185 mm).
  • the solids were suction dried overnight. HPLC, DSC, trace metals, and UV-VIS were done on a 3 gram sample of the crude product.
  • Figures 1 1 and 12 show the preparation of the isomers discussed below, and the Roman numerals in the text of this Example correspond with the Roman numerals in Figures 1 1 and 12.
  • Reichert's goal was to prepare 1 ,3,5,7- tetrakis[(4-phenylethynyl)phenyl)]adamantane of definite structure, namely, single p-isomer of this compound - 1 ,3,5,7-tetrakis[4'- (phenylethynyl)phenyl]adamantane (VIII).
  • This, and only this compound, having definite structure was the target of Reichert's work.
  • Bromobenzene is known to disproportionate essentially in the conditions of Friedel-Crafts reaction (G.A. Olah, W..S.Tolgyesi, R.E.A.Dear. J. Org. Chem., 27, 3441 - 3449 (1962)):
  • 1 ,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane (III) (that Reichert thought she synthesized) can be prepared by second treatment of the solid reaction product of 1 ,3,5,7-tetrabromoadamantane with bromobenzene in presence of aluminum bromide.
  • Trace o-isomer may also be present.
  • thermosetting component (a) which is useful as a thermosetting component (a).
  • Example 6 This example illustrates the preparation of another thermosetting monomer (a).
  • Step 1 Synthesis of m- and p-bromotolane isomers
  • Step 2 Synthesis of m- and p-Ethynyltolane
  • p-ethynyltolane was synthesized in two steps.
  • p-bromotolane was trimethylsilylethynylated using trimethylsilylacetylene (TMSA, as shown above), and in the second step, the reaction product of the first step was converted to the final end product.
  • TMSA trimethylsilylacetylene
  • Step a Trimethylsilylethynylation of 4-bromotolane: 4-Bromotolane (10.285g, 40.0mMol), ethynyltrimethylsilane (5.894g, 60.0mMol), 0.505g (0.73mMol) of dichlorobis(triphenylphosphine)palladium[ll] catalyst, 40 mL of anhydrous triethylamine, 0.214g (1 .12mMol) of copper[l] iodide, and 0.378g (1 .44mMol) of triphenylphosphine were placed into the N 2 purged, 5-Liter 4- neck round-bottom flask, equipped with an overhead mechanical stirrer, condenser, and positioned inside a heating mantle.
  • the mixture was heated to a gentle reflux (about 88 °C) and maintained at reflux for 1 .5 hours.
  • the reaction mixture became a thick black paste and was cooled.
  • Thin-layer chromatographic analysis indicated complete conversion of starting material 4-bromotolane to a single product.
  • the solids were filtered and washed with 50mL of triethylamine, mixed with 400mL of water and stirred for 30 minutes.
  • the solids was filtered and washed with 40mL of methanol.
  • the crude solid was recrystallized from 500mL of methanol. On standing, lustrous silver colored crystals settled out. They were isolated by filtration and washed with 2x 50mL of methanol. 4.662g was recovered (42.5% yield).
  • Step b (Conversion of 4-(Trimethylsilyl)ethynyltolane to 4- Ethynyltolane): To a 1 -Liter 3 neck round-bottom flask equipped with a nitrogen inlet, an overhead mechanical stirrer, was charged 800mL of anhydrous methanol, 1 2.68g (46.2mMol) of 4-(trimethylsilyl)ethynyltolane, and 1 .1 2g of anhydrous potassium carbonate. The mixture was heated to 50°C. Stirring continued until no starting material was detected by HPLC analysis (about 3 hours). The reaction mixture was cooled. The crude solids were stirred in 40mL of dichloromethane for 30 min and filtered.
  • the filtered suspended solids by HPLC showed mainly impurities.
  • the dichloromethane filtrate was dried and evaporated to yield 8.75g of a solid. On further drying in an oven, the final weight was 8.67g, which represented a yield of 92.8%.
  • Step 3 Synthesis of Mixture of 1 .3.5.7-tetrakis- ⁇ 374'-.4"- (phenylethynyl)phenylethvnyl]phenyl ⁇ adamantane (TPEPEPA) and 1 ,3/4-bis ⁇ 1 '.3'.5'-tris ⁇ 3 , 74"-r4'"- ( phenylethynyl )p henylethvnvH p henyl ⁇ adamantyl ⁇ benzene (BTPEPEPAB).
  • Thermosetting component (a) (200 grams) made from a procedure similar to that of Example 5 above was loaded into a flask. Cyclohexanone, in an amount of 5.4 times the amount of thermosetting component (a), was added to the flask and the flask was shaken.
  • the adhesion promoter (b) used was polycarbosilane (CH 2 SiH 2 ) q where q is 20-30, in an amount of 0.268 times the amount of thermosetting component (a), and was added to the flask and shaken.
  • the final solution comprised 1 5 weight percent thermosetting component (a) and 6.7 weight percent polycarbosilane adhesion promoter (b) based on thermosetting compound (a).
  • the reaction mixture was cooled to 1 20°C.
  • a Dean-Stark trap was installed and filled with toluene.
  • Toluene in an amount of 0.15 times the thermosetting component (a) amount in ml, was added to the refluxed solution. Intensive boiling and azeotroping began at 1 30°C and continued for about 40 minutes until water evolution ceased.
  • the reaction mixture temperature had increased to 148°C. Toluene and water were drained from the trap and azeotroping was continued until an additional 0.165 times the thermosetting component (a) amount of toluene and cyclohexanone were distilled.
  • the flask temperature reached 1 53-1 55°C.
  • thermosetting component (a) thermosetting component (a) and polycarbosilane component adhesion promoter (b).
  • GPC showed that an oligomer formed.
  • the following example is directed to forming a layer of the present composition and a layer of a prior art composition.
  • Comparative A is a polyarylene ether taught by Honeywell US Patent 5,986,045.
  • Example 8 the composition of Example 7 was applied to a substrate using the coating conditions in Table II:
  • BSR stands for back side rinse and EBR stands for edge bead rinse.
  • the coater used was DNS SC-W80A-A VFDLP, pressuring gas was helium, the dispense pressure was 0.08MPa, the dispense rate was 1 .Omilliliter/second, and the inline filter was 0.1 micron PFFVO1 D8S (Millipore, Fuluoroline-S).
  • the resulting spun-on composition was baked for one minute under N 2 ( ⁇ 50 ppm O 2 ) at each of the following temperatures: 1 50°C, 200°C, and 250°C.
  • the furnace cure condition was 400°C for 60 minutes in N 2 (1 5 liters/minute) with ramping up from 250°C at 5°K per minute.
  • the cure temperature range was from 350°C to 450°C.
  • a hot plate cure condition at 350°C to 450°C for 1 -5 minutes in N 2 may be used.
  • Comparative B was 100% thermosetting compound (a) and thus, did not contain adhesion promoter (b).
  • Example 8 was followed to produce the compositions of Table IV except that the amount of polycarbosilane adhesion promoter (b) was varied.
  • the polycarbosilane component (b) used was (CH 2 SiH 2 ) q where q is 20 to 30.
  • compositions and methods to produce a low dielectric constant polymer have been disclosed. It should be apparent, however, to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the appended claims. Moreover, in interpreting both the specification and the claims, all terms should be interpreted in the broadest possible manner consistent with the context. In particular, the terms “comprises” and “comprising” should be interpreted as referring to elements, components, or steps in a nonexclusive manner, indicating that the referenced elements, components, or steps may be present, or utilized, or combined with other elements, components, or steps that are not expressly referenced.

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Abstract

L'invention concerne une composition comprenant: (a) un composant thermodurcissable comprenant un monomère ayant la structure (I) et un dimère ayant la structure (II), ou un mélange du monomère et du dimère, où Y est sélectionné à partir d'un composé cage; R1, R2, R3, R4, R5, et R6 sont sélectionnés, indépendamment, à partir d'un aryle, aryle ramifié et éther d'arylène ; au moins l'un des groupes aryle, aryle ramifié et éther d'arylène étant un groupe éthynyle ; R7 désigne un aryle ou un aryle substitué ; et au moins l'un des R1, R2, R3, R4, R5, et R6 comprend au moins deux isomères ; (b) un promoteur d'adhérence comprenant un composé ayant au moins une bifonctionnalité, cette dernière pouvant être la même ou différente, la première fonctionnalité étant capable d'entrer en interaction avec le composant thermodurcissable (a) et la seconde fonctionnalité étant capable d'entrer en interaction avec un substrat lorsque la composition est appliquée sur un substrat. La composition selon l'invention est utilisée notamment comme matériau diélectrique pour des applications en micro-électronique.
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US7790234B2 (en) 2006-05-31 2010-09-07 Michael Raymond Ayers Low dielectric constant materials prepared from soluble fullerene clusters
JP2008109061A (ja) * 2006-09-29 2008-05-08 Matsushita Electric Ind Co Ltd リード、配線部材、パッケージ部品、樹脂付金属部品及び樹脂封止半導体装置、並びにこれらの製造方法
US7638566B2 (en) * 2006-10-30 2009-12-29 Sabic Innovative Plastics Ip B.V. Poly(arylene ether) compositions
GB2451865A (en) 2007-08-15 2009-02-18 Univ Liverpool Microporous polymers from alkynyl monomers
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