JP2005514479A - Organic composition - Google Patents

Abstract

The composition of the present invention comprises (a) a monomer having a structure, a dimer having a structure, or a mixture of the monomer and the dimer (wherein Y is selected from a cage compound and a silicon atom, and R ₁ , 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, branched aryl, and arylene ether has an ethynyl group; R ₇ is aryl or substituted aryl, and at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ has at least two isomers) And (b) an adhesion promoter comprising at least a bifunctional compound, wherein the bifunctional may be the same or different, The potential is capable of interacting with the thermosetting component (a), when the composition is applied to a substrate, the second functionality may provide the substrate can interact and which composition. The compositions of the present invention are particularly useful as dielectric materials for microelectronic applications.

Description

  The present invention relates to a semiconductor device, and more particularly to a semiconductor device having an organic low dielectric constant material and a method for manufacturing the same.

  In an attempt to improve the performance and speed of semiconductor devices, semiconductor device manufacturers have attempted to minimize transmission loss and reduce interconnect capacitive coupling while reducing interconnect linewidth and spacing. One way to reduce power consumption and reduce capacitance is to reduce the dielectric constant (also referred to as “k”) of the insulating material or dielectric that separates the wires. Insulating materials with low dielectric constants are particularly desirable because they generally speed up signal propagation, reduce crosstalk between capacitance and conductors, and require lower voltages to drive integrated circuits.

  Since the dielectric constant of air is 1.0, the main purpose is to reduce the dielectric constant of the insulating material to the theoretical limit of 1.0, and several methods for reducing the dielectric constant of the insulating material are known. It is. These methods include adding an element such as fluorine to the bulk material to reduce the overall dielectric constant of the material. Other methods for reducing k include the use of alternating dielectric material matrices.

  Therefore, when reducing the line width of the wiring, it is necessary to reduce the dielectric constant of the insulating material accordingly, thereby achieving the desired performance and speed improvements in future semiconductor devices. For example, in a device in which the line width of the wiring is 0.13 μm or 0.10 μm and less, an insulating material having a dielectric constant (k) <3 is required.

Currently, SiO ₂ modified materials such as silicon dioxide (SiO ₂ ) and fluorinated silicon dioxide or fluorinated silicon glass (hereinafter referred to as FSG) are used. These oxides (dielectric constants ranging from about 3.5 to 4.0) are often used as dielectrics in semiconductor devices. Although SiO ₂ and FSG have the mechanical and thermal stability necessary to withstand the thermal cycling and processing steps of semiconductor device manufacturing, there is a need for lower dielectric constant materials in this field.

  The methods used to deposit the dielectric material can be classified into two types: spin-on deposition (hereinafter referred to as SOD) and chemical vapor deposition (hereinafter referred to as CVD). Attempts to develop materials with lower dielectric constants include changing the chemical composition (organic, inorganic, organic / inorganic mixtures) or changing the dielectric matrix (porous, non-porous). Table I summarizes the development of several materials with dielectric constants ranging from 2.0 to 3.5 (PE = plasma assist, HDP = high density plasma). However, the dielectric materials and matrices disclosed in the publications listed in Table 1 have higher mechanical stability, high thermal stability, high glass transition temperature, high modulus or hardness, and at the same time a substrate, It does not combine many of the physical and chemical properties that are sometimes required for effective dielectric materials that can be solubilized, spin-coated, or deposited on a wafer or other surface. Thus, although it may be a compound or material that is not considered a dielectric material in its current form, it would be useful to study other compounds and materials that can be used as dielectric materials and layers.

  Unfortunately, many organic SOD systems under development that have a dielectric constant between 2.0 and 3.5 have drawbacks with respect to the mechanical and thermal properties described above, and thus dielectrics in this dielectric constant range. Developments to improve the processability and performance of conductive films continue to be needed in the art.

  Reichert and Mathias describe compounds and monomers that contain adamantane molecules, which are a class of cage molecules and are considered useful as diamond replacements (Polym, Prepr. (Am. Chem). Soc., Div.Polym.Chem.), 1993, 34 (1), pages 495-6; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1992, 33 (2). ), 144-5; Chem. Mater., 1993, 5 (1), 4-5; Macromolecules, 1994, 27 (24), 7030-7034; Macromolecules, 1994, 27 (24). , 7015-70 3 pages; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1995, 36 (1), pages 741-742; 205th ACS National Conference, Conference Program (205th ACS National Meeting) , Conference Program), 1993, 312; Macromolecules, 1994, 27 (24), 7024-9; Macromolecules, 1992, 25 (9), 2294-306; Macromolecules, 1991, 24 (18). Veronica R. Reichert, PhD Dissertation, 1994, 55-06B, Vol. ACS Symp. Ser .: Step-Growth Polymers for High-Performance Materials, 1996, 624, 197-207; Macromolecules, 2000, 33 (10) , 3855-3859; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1999, 40 (2), pages 620-621; Polym, Prepr. (Am. Chem. Soc. , Div.Polym.Chem.), 1999, 40 (2), 577-78; Macromolecules, 1997, 30 (19), 5970-5975; Polym. Sci, Part A: Polymer Chemistry, 1997, 35 (9), pages 1743-1751; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1996, 37 (2), pages 243-244; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1996, 37 (1), 551-552; Polym. Sci. , Part A: Polymer Chemistry, 1996, 34 (3), pages 397-402; Polym, Prepr. (Am. Chem, Soc., Div. Polym. Chem.), 1995, 36 (2), pages 140-141; Polym, Prepr. (Am, Chem. Soc., Div. Polym. Chem.), 1992, 33 (2), pages 146-147; Appl. Polym. Sci. 1998, 68 (3), pages 475-482). The adamantane compounds and monomers described by Reichert and Mathias are preferably used to produce polymers having adamantane molecules in the core of the thermosetting material. However, the compounds disclosed in Reichert and Mathias studies contain only one isomer of adamantane compounds by design choice. Structure A represents this symmetric para isomer 1,3,5,7-tetrakis [4 '-(phenylethynyl) phenyl] adamantane:

Is shown.

In other words, Reichert and Mathias individual studies and collaborative studies have considered useful polymers containing only one isomer of the targeted adamantane monomer. However, when a polymer is produced from one isomer of an adamantane monomer (a symmetric “all para” isomer) 1,3,5,7-tetrakis [4 ′-(phenylethynyl) phenyl) adamantane and processed There is a big problem. According to Reichert's doctoral dissertation (supra) and Macromolecules, 27, (pages 7015-7034) (supra), the symmetric all para isomer 1,3,5,7-tetrakis [4 '-(phenylethynyl] ) Phenyl] adamantane was found to be sufficiently soluble in chloroform to give a ¹ H NMR spectrum. However, the time required to obtain the solution ¹³ C NMR spectrum proved impractical and it can be said that the solubility of all para isomers is lower. Therefore, Reichert's symmetrical “all para” isomers 1,3,5,7-tetrakis [4 ′-(phenylethynyl) phenyl] adamantane are insoluble in standard organic solvents and therefore need solubility It is not useful for applications such as, or solvent-based processing methods such as flow coating, spin coating, or dip coating. See Comparative Example 1 below.

  In a continuation patent application PCT / US01 / 22204 (filed Oct. 17, 2001) assigned to the same assignee as the present application, we have described a composition comprising an isomer thermosetting monomer or dimer mixture. Discover and mix this structure

Wherein Y is selected from a cage compound and a silicon atom, 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, and R ₇ is aryl or substituted aryl). The inventors also disclose a method for producing these thermosetting mixtures. This novel isomeric thermosetting monomer or dimer mixture is useful as a dielectric material for microelectronic applications and is soluble in many solvents such as cyclohexanone. Because of these desirable properties, this isomeric thermosetting monomer or dimer mixture is ideal for film formation from about 0.1 μm to about 1.0 μm thick.

  Various methods for reducing the dielectric constant of materials are known, but these methods have drawbacks. Thus, in the semiconductor industry, a) provision of improved compositions and methods for reducing the dielectric constant of dielectric layers, b) improved mechanical properties such as thermal stability, glass transition temperature (Tg), and hardness. There is a continuing need to provide such dielectric materials, and c) the production of thermosetting compounds and dielectric materials that are solvable and spin-on on a wafer or layered material.

  In response to the need in the art, we have (a) a structure

Monomer having structure

Or a mixture of the monomer and the dimer, wherein Y is selected from a cage compound and a silicon atom, and 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 said aryl, said branched aryl, and said arylene ether has an ethynyl group, R ₇ is aryl or substituted aryl, said R ₁ , R ₂ , At least one of R ₃ , R ₄ , R ₅ , and R ₆ has at least two isomers),
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting component (a), and the composition is applied to a substrate In some cases, a second functionality has been developed that is capable of interacting with the substrate.

Preferably the adhesion promoter is
(I) Formula (I):

Wherein each of R ₈ , R ₁₄ , and R ₁₇ independently represents a substituted or unsubstituted alkylene, cycloalkylene, vinylene, arylene, or arylene, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene, and may be linear or branched, and R ₁₃ is organosilicon, silanyl, siloxyl Or a, b, c, and d satisfy the condition [4 ≦ a + b + c + d ≦ 100,000], and b, c, and d may all be 0, or may be independently 0 There are also polycarbosilanes,
(Ii) Formula (R ₁₈ ) _f (R ₁₉ ) _g Si (R ₂₀ ) _h (R ₂₁ ) _i (wherein R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently hydrogen, hydroxyl, Represents unsaturated or saturated alkyl, substituted or unsubstituted alkyl, and the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid group, or aryl, R ₁₈ , R ₁₉ , R ₂₀ , And at least two of R ₂₁ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid group, f + g + h + i ≦ 4)
(Iii) formula _{- [R 22 C 6 H 2} (OH) (R 23)] j - ( _{wherein, R 22} is a substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl or _{aryl,, R 23} Is alkyl, alkylene, vinylene, cycloalkylene, arylene, or aryl, and j = 3-100), phenol-formaldehyde resin or oligomer,
(Iv) glycidyl ether,
(V) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group, and (vi) a vinyl cyclic oligomer or polymer in which the cyclic group is pyridine, aromatic, or heteroaromatic,
Selected from the group consisting of

The inventors have
(A) Structure

Monomer having structure

Or a mixture of the monomer and the dimer wherein Y is selected from a cage compound and a silicon atom, and 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 said aryl, said branched aryl, and said arylene ether has an ethynyl group, R ₇ is aryl or substituted aryl, said R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ have at least two isomers), and
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting component (a), and the second functionality is with the substrate. A method for improving adhesion to a substrate has also been developed, including the step of applying a layer comprising a composition capable of interaction to the substrate.

  In addition, the inventors have (a) a structure

Wherein Ar is aryl and R ′ ₁ , R ′ ₂ , R ′ ₃ , R ′ ₄ , R ′ ₅ , and R ′ ₆ are independently aryl, branched aryl, arylene ether, and unsubstituted. And each of the aryl, the branched aryl, and the arylene ether has at least one ethynyl group), and
(B) an adhesion promoter comprising at least a bifunctional compound;
The bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting monomer (a), and the composition is applied to a substrate. In some cases, a composition was also developed in which the second functionality is capable of interacting with the substrate. Preferably, the adhesion promoter (b) comprises (i) polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (iv) glycidyl ether, (v) unsaturated carboxylic acid ester, Or (vi) selected from vinyl cyclic oligomers or polymers.

The present inventors also provide a method for producing a low dielectric constant polymer precursor,
(1) (a) Structure

Monomer having structure

Or a mixture of the monomer and the dimer wherein Y is selected from a cage compound and a silicon atom, and 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 said aryl, said branched aryl, and said arylene ether has an ethynyl group, R ₇ is aryl or substituted aryl, said R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ have at least two isomers), and
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting component (a), and the composition is applied to a substrate Providing a composition wherein the second functionality is capable of interacting with the substrate;
(2) generating the low dielectric constant polymer precursor by treating the composition at a temperature of about 30 ° C. to about 350 ° C. for about 0.5 hours to about 60 hours;
We have also developed a method that includes Preferably, the adhesion promoter (b) comprises (i) polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (iv) glycidyl ether, (v) unsaturated carboxylic acid ester, Or (vi) selected from vinyl cyclic oligomers or polymers.

The present inventors also provide a method for producing a low dielectric constant polymer,
(1) (a) Structure

Monomer having structure

Or a mixture of the monomer and the dimer wherein Y is selected from a cage compound and a silicon atom, and 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 said aryl, said branched aryl, and said arylene ether has an ethynyl group, R ₇ is aryl or substituted aryl, said R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ have at least two isomers), and
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting component (a), and the composition is applied to a substrate And wherein the second functionality provides an oligomer capable of interacting with the substrate;
(2) A method for producing a low dielectric constant polymer was also developed, which comprises a step of producing the low dielectric constant polymer by polymerizing the oligomer, wherein the polymerization comprises a chemical reaction of the ethynyl group. Preferably, the adhesion promoter (b) comprises (i) polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (iv) glycidyl ether, (v) unsaturated carboxylic acid ester, Or (vi) selected from vinyl cyclic oligomers or polymers.

The inventors also (a) a first main chain having a first aromatic moiety and a first reactive group, a second aromatic moiety and a second having a second reactive group. A main chain (the first and second main chains are cross-linked by the first and second reactive groups in a cross-linking reaction), and a cage type covalently bonded to at least one of the first and second main chains An adhesion promoter comprising a structure (wherein the cage structure has at least 8 atoms), and (b) a compound that is at least bifunctional;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the first and second backbones, and the material is a substrate A spin-on low dielectric constant material has also been developed in which the second functionality is capable of interacting with the substrate when applied to. Preferably, the adhesion promoter (b) comprises (i) polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (iv) glycidyl ether, (v) unsaturated carboxylic acid ester, Or (vi) selected from vinyl cyclic oligomers or polymers.

  Various objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the invention and the accompanying drawings.

  As used herein, the term “at least two isomers” means at least two isomers selected from meta isomers, para isomers, and ortho isomers. Preferably, the at least two isomers are meta isomers and para isomers.

  As used herein, the term “low dielectric constant polymer” means an organic, organometallic, or inorganic polymer having a dielectric constant of about 3.0 or less. In many cases, the low dielectric material is manufactured in the form of a thin layer with a thickness of 100 to 25,000, but can also be used as a thick film, block, cylinder, or sphere.

  In addition, as used herein, the term “main chain” means a chain in which atoms or portions forming a polymer chain are continuous, and the removal of a part of these atoms or portions breaks the chain. Thus, some of these atoms or moieties are covalently bonded.

  As used herein, the term “reactive group” refers to an atom, functional group, or group that is sufficiently reactive to form at least one covalent bond with another reactive group by a chemical reaction. means. A chemical reaction may occur with two identical or different reactive groups, which may be present on the same backbone or on two independent backbones. It is also contemplated that the first and second backbones can crosslink by reacting with one or more second or external crosslinkable molecules. Crosslinking without the use of an external crosslinker has various advantages, such as reducing the total number of reactive groups in the polymer and reducing the number of reaction steps required. There are also disadvantages. For example, it is usually impossible to adjust the amount of the crosslinkable functional group. On the other hand, the use of an external cross-linking agent can be advantageous when the polymerization reaction and the cross-linking reaction are chemically incompatible.

  Further, as used herein, the phrases “cage structure”, “cage molecule”, and “cage compound” are intended to be used interchangeably, and these terms are: A molecule having at least 8 atoms arranged such that at least one bridging moiety is covalently bonded to 2 or more atoms of the ring structure. In other words, a cage structure, cage molecule, or cage compound includes multiple rings formed by covalently bonded atoms, and these structures, molecules, or compounds define a volume within that volume. A point cannot leave its volume without passing through the ring. Bridges and / or ring structures may contain one or more heteroatoms and contain aromatic groups, partially cyclic or acyclic saturated hydrocarbon groups, or cyclic or acyclic unsaturated hydrocarbon groups. Good. Furthermore, the cage structure of the present invention also includes fullerenes and crown ethers having at least one bridge. For example, adamantane or diamantane is considered a cage structure, and naphthalene or aromatic spiro compounds are not considered a cage structure by this definition. Because it does not have one or more cross-links of naphthalene or aromatic spiro compounds and is therefore not included in the scope of the cage-type compounds described above.

  As used herein, the phrase “adhesion promoter” refers to a substrate when added to a thermosetting component (a) or polymer rather than to the thermosetting component (a) alone or the polymer alone. It means an optional component that improves the adhesiveness of. As used herein, the phrase “at least bifunctional compound” means any compound having at least two functional groups capable of interaction, reaction, or bond formation, as described below. Functional groups can react in a number of ways, including addition reactions, nucleophilic and electrophilic substitutions or eliminations, radical reactions and the like. Yet another reaction may include the formation of non-covalent bonds such as van der Waals bonds, electrostatic bonds, ionic bonds, and hydrogen bonds.

As used herein, the term “layer” includes films and coatings.
(Thermosetting component (a))
Thermosetting component (a) and polymer are assigned to the same assignee as the present application and are pending US patent application Ser. No. 09/618945 (filed Jul. 19, 2000), US patent application Ser. No. 09/879936 ( Filed July 5, 2001), PCT / US01 / 22204 (filed October 17, 2001), U.S. Patent Application No. 09/545058 (filed April 7, 2000), and U.S. Patent Application No. 09 / 902924) (submitted July 10, 2001), all of which are incorporated herein.

  Thermosetting component (a) has structure 1A

A monomer having the general structure shown in Structure 1B

Or a mixture of these monomers and dimers, wherein Y is selected from a cage compound and a silicon atom, R ₁ , 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, branched aryl, and arylene ether has an ethynyl group. R ₇ is aryl or substituted aryl, in which case the substituent is alkyl, halogen, or aryl. As used herein, unless the term “aryl”, which is further specified, is further specified, the term means any type of aryl that may include branched aryl or arylene ethers and the like. Preferably Y is adamantane or diamantane. Representative structures of thermosetting monomers having adamantane, diamantane, and silicon atoms are shown in FIGS. 1A, 1B, and 1C, respectively, where n is an integer from 0 to 5 or greater. Representative structures of thermosetting dimers having adamantane and diamantane are shown in FIGS. 1D and 1E, respectively, where n is an integer from 0 to 5 or greater. Preferably, a mixture of these monomers and dimers is present in the thermosetting component (a). Preferably, the mixture comprises about 95% to 97% by weight monomer and about 3-5% by weight dimer.

  Alternatively, the thermosetting monomer (a) has the structure 2:

In which Ar is aryl and R ′ _{1 to} R ′ ₆ are independently selected from aryl, branched aryl, arylene ether, and unsubstituted, and these aryl, branched aryl And each of the arylene ethers has at least one ethynyl group. Representative structures of thermosetting monomers having 4-substituted sexiphenylene and 6-substituted sexiphenylene are shown in FIGS. 2A to 2B and 2C to 2D, respectively.

  Thermosetting monomers generally shown in structures 1A and 1B and 2 can be prepared by a variety of synthetic routes, and exemplary synthetic schemes for structures 1A and 1B and 2 are shown in FIGS. 3A-3C. Illustrated in FIG. 3A and illustrated in Example 5 is a preferred synthesis route for the thermoplastic monomer of the present invention having adamantane as the cage compound, in which a Heck reaction using a palladium catalyst is performed. To phenylethynylate bromoallene. First, the adamantane (1) is bromo-modified according to conventional procedures (Solot, GP, and J. Org. Chem. 45, 5405-5408 (1980) by Gilbert, EE). To produce 1,3,5,7-tetrabromoadamantane (TBA) (2). Reichert, V.M. R, and Mathias L. J. et al. Macromolecules, 27, 7015-7022 (1990) by reacting TBA with phenyl bromide to produce 1,3,5,7-tetra (3 ′ / 4′-bromophenyl) adamantane ( TBPA) (3), followed by reaction with TBPA-substituted ethynylaryl by a Heck reaction using a palladium catalyst, followed by standard reaction procedures to obtain 1,3,5,7-tetrakis [3 / 4- (Arylethynyl) phenyl] adamantane (4) is produced. Example 5 illustrates Reichert's work and compounds described in "Background" and the difference between the compound and the thermosetting component (a) of the present invention. The Heck reaction using a palladium catalyst can also be used to synthesize thermosetting monomers having sexiphenylene as an aromatic moiety as shown in FIGS. 2A to 2D, in which case tetrabromosethoxyphenylene and hexa Reaction of bromocenylphenylene with an ethynylaryl compound produces the desired corresponding thermosetting monomer.

In another method, TBA can be converted to hydroxyarylated adamantane, from which a thermosetting monomer is obtained by a nucleophilic aromatic substitution reaction. In FIG. 3B, TBA (2) is generated from adamantane (1) as described above and is further subjected to electrophilic tetrasubstitution with phenol to give 1,3,5,7-tetrakis (3 ′ / 4′-hydroxyphenyl). Adamantane (THPA) (5) is produced. Alternatively, TBA is reacted with anisole to produce 1,3,5,7-tetrakis (3 ′ / 4′-methoxyphenyl) adamantane (6), which is further reacted with BBr ₃ to produce THPA (5). It can also be generated. Second, THPA follows standard procedures (eg, Engineering Plastics-A Handbook of Polyarylethers by RJ Cotter, Gordon & Bleach Publishers, Gordon). and Breach Publishers), ISBN 2-88449-112-0) in the presence of calcium carbonate to react with various nucleophilic aromatic substitution reactions to produce the desired thermosetting monomer. Or THPA can be reacted with 4-halo-4′-fluorotolane (halo = Br or I) in standard aromatic substitution reactions (eg, “Engineering Plastics”, supra). To produce 1,3,5,7-tetrakis {3 ′ / 4 ′-[4 ″-(halophenylethynyl) phenoxy] phenyl} adamantane (7). In yet another reaction, A variety of different reactants can be used to produce thermosetting monomers, as well as nucleophilic aromatic substitution reactions can be used to synthesize thermoplastic monomers with sexiphenylene as the aromatic moiety. In this reaction, sexiphenylene is reacted with 4-fluorotolane to produce a thermosetting monomer, or phloroglucinol is converted to 4- [4 ′-(fluorophenylethynyl) by a standard aromatic substitution reaction. Phenylethynyl] benzene is reacted to produce 1,3,5-tris {4 ′-[4 ″-(phenylethynyl) phenylethynyl] phenoxy} benzene Can.

  A typical preferred synthesis scheme when the cage compound is a silicon atom is shown in FIG. 3C, according to which the bromo (phenylethynyl) aromatic arm (8) (where n is 0 to 0). 5 or greater) is converted to the corresponding (phenylethynyl) aryllithium arm (9), which is then reacted with silicon tetrachloride to produce the desired star with silicon atoms as cage compounds. A thermosetting monomer (10) is formed.

Preferably, the cage compound is a silicon atom, adamantane, diamantane, or a plurality of adamantane or diamantane. In another aspect of the invention, various cage compounds other than adamantane and diamantane are also contemplated. Depending on the molecular size and configuration of the cage compound and the overall length of the arms R _{1 to} R ₆ or R ′ _{1 to} R ′ ₆ , some physical and mechanical properties of the final low dielectric constant polymer It should be particularly understood that is determined (by steric effects). Thus, where relatively small cage compounds are desired, substituted and derivatized adamantane, diamantane, and relatively small bridged cycloaliphatic and aromatic compounds (usually less than 15 atoms) are also considered. In contrast, where larger cage compounds are desired, larger bridged cycloaliphatic and aromatic compounds (usually having more than 15 atoms) and fullerenes are considered.

The cage compound of the present invention is not necessarily limited to the constitution with only carbon atoms, and may contain heteroatoms such as N, S, O and P. Heteroatoms may be advantageous for introducing bond angle structures that are not square, which allows for covalent bonding of arms R _{1 to} R ₆ or R ′ _{1 to} R ′ ₆ . It should be understood that many substituents and derivatives are suitable for the substituents and derivatization of the cage compounds of the present invention. For example, if the cage compound is relatively hydrophobic, a hydrophilic substituent can be introduced to improve solubility in a hydrophilic solvent, or vice versa. Thus, if polarity is desired, polar side groups can be introduced into the cage compound. Suitable substituents can further include thermally labile groups, as well as nucleophilic and electrophilic groups. It is also preferred that the functional group be available within the cage compound (eg, to promote cross-linking reaction, derivatization reaction, etc.). When a cage compound is derivatized, what is particularly considered for derivatization is halogenation of the cage compound, and particularly preferred halogens are fluorine and bromine.

When the thermosetting monomer (a) has an aryl bonded to the arms R ′ _{1 to} R ′ ₆ as shown in structure 2, it is preferred that the aryl comprises a phenyl group, even more preferably the aryl is Contains a phenyl group that produces sexiphenylene. In another aspect of the invention, various aryl compounds other than phenyl groups (or sexiphenylene) are also suitable, such as substituted and unsubstituted bicyclic and polycyclic aromatic compounds. Is mentioned. Substituted and unsubstituted bicyclic and polycyclic aromatic compounds are particularly advantageous when enlargement of thermosetting monomers is preferred. For example, naphthalene, phenanthrene, and anthracene are specifically considered when it is desired that the alternative aryl extend in one direction than the other. Where it is desirable for the alternative aryl to extend symmetrically, a polycyclic aryl such as coronene is contemplated. In preferred embodiments, the bicyclic and polycyclic aryls considered have conjugated aromatic systems that may or may not contain heteroatoms. The same considerations apply for the aryl substitutions and derivatizations considered as for the caged compounds described herein.

With respect to the arms R _{1 to} R ₆ or R ′ _{1 to} R ′ ₆ , R _{1 to} R ₆ are preferably independently selected from aryl, branched aryl, and arylene ether, and R ′ _{1 to} R ′ ₆ are independently Are preferably selected from aryl, branched aryl, and arylene ethers, and no substitution. Aryl specifically contemplated for R ₁ -R ₆ and R ′ ₁ -R ′ ₆ include (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and aryl having a (phenylethynyl) phenylphenyl moiety. . Particularly preferred arylene ethers include (phenylethynylphenyl) phenyl ether. Aryl specifically contemplated as R ₇ is phenyl and substituted aryl such as phenyl substituted with hydrogen, alkyl, aryl, or halogen.

In another aspect of the invention, if the arms R _{1 to} R ₆ and R ′ _{1 to} R ′ ₆ contain reactive groups and the polymerization of the thermosetting component contains a reaction involving reactive groups, The appropriate arms of the curable component need not be limited to aryls, branched aryls, and arylene ethers. For example, the arms considered may be relatively short with 6 or fewer atoms, which may or may not be carbon atoms. Such short arms can be particularly advantageous when voids or pores are desired in the final product or material and the required pore size is relatively small. In contrast, if a particularly long arm is preferred, the arm may comprise an oligomer or polymer having from 7 to 40 or more atoms. These long arms may be advantageous over shorter arms when intended for material stability, thermal stability, or porosity. Furthermore, the length and chemical composition of the arm covalently bonded to the intended thermosetting monomer may vary in one type of monomer. For example, a cage compound may have two relatively short arms and two relatively long arms to facilitate dimensional increase in a particular direction during polymerization. In another example, the cage compound may have two arms that are chemically different from the other two arms to facilitate the regioselective derivatization reaction.

Although it is preferred that all arms of the thermosetting component have at least one reactive group, in another embodiment, not all arms need to have a reactive group. For example, the cage compound may have 4 arms and only 3 or 2 arms may have a reactive group. Alternatively, the aryl in the thermosetting component has 3 arms, of which only 2 or 1 arm may have a reactive group. Depending on the chemistry of the arm and the desired end product quality, the number of reactive groups on each of the arms R _{1 to} R ₆ and R ′ _{1 to} R ′ ₆ can often vary greatly. . Furthermore, a reactive group may be present in any part of the arm including the main chain, side chain, or end of the arm. Of particular note, the number of reactive groups in the thermosetting component (a) can be used as a tool to adjust the degree of crosslinking. For example, if a relatively low degree of crosslinking is desired, the thermoset monomers considered have only one or two reactive groups, which may or may not be present on a single arm. On the other hand, if a relatively high degree of crosslinking is required, more than two reactive groups may be present in the monomer. Preferred reactive groups include electrophilic groups and nucleophilic groups, more preferred groups are groups that can participate in cycloaddition reactions, and particularly preferred reactive groups are ethynyl groups.

  In addition to the reactive group in the arm, other groups such as a functional group may be included in the arm. For example, if it is desired that a particular functionality (eg, a thermolabile moiety) be imparted after polymerizing a thermosetting monomer into a polymer, such functionality can be covalently attached to the functional group.

  The thermosetting component (a) can be polymerized by many types of mechanisms, and the actual mechanism of polymerization mainly depends on the reactive groups involved in the polymerization process. Thus, the mechanisms considered include nucleophilic, electrophilic, and aromatic substitution reactions, addition reactions, elimination reactions, radical polymerization reactions, and cycloaddition reactions, and particularly preferred polymerization mechanisms are: Cycloaddition involving at least one ethynyl group present in at least one arm. For example, when the thermosetting component (a) has an arm selected from aryl, branched aryl, and arylene ether, and at least three of these aryl, branched aryl, and arylene ether have one ethynyl group, Polymerization of the curable component (a) can include a cycloaddition reaction (ie, chemical reaction) of at least two ethynyl groups. In another example, if the aryl, branched aryl, and arylene ether arms are all thermosetting monomers (a) having one ethynyl group, the polymerization process may be a cycloaddition reaction (ie, chemical reaction) of these ethynyl groups. ). In another example, the cycloaddition reaction (eg, the Diels-Alder reaction) is performed between the ethynyl group of at least one arm of the thermosetting monomer (a) and the diene group present in the polymer. Can happen between. Furthermore, the polymerization of the thermosetting component (a) can be carried out without using another molecule (for example, a crosslinking agent), and in the cycloaddition reaction between the reactive groups of the thermosetting monomer (a). This is preferred. However, in another aspect of the present invention, a crosslinking agent can be utilized to covalently bond the thermosetting component (a) to produce a polymer. Such covalent bonding can occur either between the reactive group and the polymer or between the functional group and the polymer.

  Depending on the polymerization mechanism of the thermosetting component (a), the reaction conditions can vary greatly. For example, if the monomer is polymerized in a cycloaddition reaction using at least one arm ethynyl group, heating the thermosetting monomer to about 250 ° C. or more for about 45 minutes is often sufficient. In contrast, if the monomer is polymerized by a radical reaction, the addition of a radical initiator may be appropriate. Preferred polymerization methods and techniques are described in the examples.

  The thermosetting component may be present at any position in the polymer backbone including the ends, or may be present as a polymer side chain.

  Polymers considered include a wide variety of polymers such as polyimide, polystyrene, polyamide and the like. However, particularly contemplated polymers include polyarylene, more preferably poly (arylene ether). In an even more preferred embodiment, it is specifically contemplated that the polymer is produced at least in part from a thermosetting monomer and entirely from isomers of the thermosetting component.

  In the particularly considered arm extension method shown in FIG. 4 (Ad represents an adamantane or diamantane group), phenylacetylene is the starting material, which is reacted with TBPA (supra) ( 1) 1,3,5,7-tetrakis [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane (TPEPA) is produced. Alternatively, phenylacetylene is converted to 4- (phenylethynyl) phenylbromide (2), which is then reacted with trimethylsilylacetylene (TMSA) (3) to produce 4- (phenylethynyl) phenylacetylene. Next, TBPA is reacted with 4- (phenylethynyl) phenylacetylene (4) and 1,3,5,7-tetrakis {3 ′ / 4 ′-[4 ″-(phenylethynyl) phenylethynyl] phenyl} In a further extension reaction, 4- (phenylethynyl) phenylacetylene can be reacted with 1-bromo-4-iodobenzene (5) to give 4- [4 ′-(phenylethynyl). ) Phenylethynyl] phenyl bromide, which is further converted to 4- [4 ′-(phenylethynyl) phenylethynyl] acetylene (6), thus synthesized 4- [4 ′-(phenylethynyl) phenylethynyl. Acetylene is reacted with TBA (7) to give 1,3,5,7-tetrakis- {3 '/ 4'-[4 " Can generate - (4 '' (phenylethynyl) phenylethynyl) phenylethynyl] phenyl} adamantane.

The present invention relates to (a) a polymer having a pendant cage structure— [OR ₂₄ (R ₂₅ ) _m OR ₂₆ ] n— (wherein R ₂₄ is —C ₆ H ₃ , R ₂₅ is adamantane, diamantane, a _(C 6 _H 5) p (adamantane), or _{(C 6 H} 5) p _{(diamantane),} an m = 1 to 3, a n = 1 to 10 ^3, a p = 0 or 1, R ₂₆ represents 2,3,4,5- (tetraphenyl) cyclodienone-1 or

Base)
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the polymer having the pendant cage structure, and the composition is applied to the substrate When applied, the second functionality also provides a spin-on low dielectric constant polymer that can interact with the substrate. Preferably, the adhesion promoter (b) comprises (i) polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (iv) glycidyl ether, (v) unsaturated carboxylic acid ester, Or (vi) selected from vinyl cyclic oligomers or polymers.

  As described above, the present invention provides (a) a first main chain having a first aromatic moiety and a first reactive group, a second aromatic moiety and a second having a second reactive group. (The first and second main chains are cross-linked by the first and second reactive groups in a cross-linking reaction), and a cage covalently bonded to at least one of the first and second main chains A spin-on low dielectric constant material comprising: a mold structure (wherein the cage structure has at least 8 atoms); and (b) an adhesion promoter comprising a compound that is at least difunctional. The first functionality can interact with the first and second backbones, and when the composition is applied to a substrate, the second functionality is with the substrate. Also provided are spin-on low dielectric constant materials that are capable of interacting.

  As shown in structures 3A to B (only one repeat unit of the main chain is shown), at least one main chain is a poly (arylene ether) having two pendant adamantane groups each as a cage structure. May include. Preferred cross-linking conditions are to heat the poly (arylene ether) backbone to a temperature of about 200 ° C. to 250 ° C. or higher for about 30 minutes to 180 minutes. Structure 3B can be synthesized by the method outlined in Examples 1 to 3 below.

  The first and second aromatic moieties comprise phenyl groups, and the first and second reactive groups are each ethynyl, tetracyclone, or both ethynyl and tetracyclone moieties, and these groups are Diels-Alder The main chain is cross-linked by the reaction.

In another embodiment, the backbone need not be limited to poly (arylene ether) and can vary greatly depending on the physicochemical properties desired in the final low dielectric constant material. Thus, inorganic materials such as inorganic polymers including silicates (SiO ₂ ) and / or aluminates (Al ₂ O ₃ ) are specifically considered when a relatively high Tg is desired. Organic polymers are considered where flexibility, ease of processing, or low stress / TCE are required. For example, depending on the particular application, the organic backbones considered include polyimides, polyamides, and polyesters.

  The chain length of the first and second polymer main chains is preferably composed of a low molecular weight polymer having a molecular weight of about 1000 to 10,000, but varies from 5 or less to tens of thousands or more. You can do it. A preferred backbone is synthesized from the monomer by an aromatic substitution reaction and examples of synthetic routes are shown in FIGS. Further, in some cases, the main chain may be branched, highly branched, or at least partially cross-linked. Alternatively, the backbone may be synthesized in situ from the monomer. Suitable monomers preferably include aromatic bisphenol compounds and difluoroaromatic compounds, which may incorporate from 0 to about 20 cage structures.

Suitable thermosetting components (a) may also have a tetrahedral structure as outlined in structures 1A and 1B or 4A and 4B. In the general structures 1A and 1B, the thermosetting monomer has a cage structure Y, at least two of the side chains R _{1 to} R ₆ have an aromatic moiety and a reactive group, and at least one of the first monomers One reactive group reacts with at least one reactive group of the second monomer to produce a low dielectric constant polymer. In the general structure 4A, a cage structure (preferably adamantane) is bonded to four aromatic moieties that can participate in polymerization, and R _{1 to} R ₄ in the formula may be the same or different. At least one of R ₁ , R ₂ , R ₃ , and R ₄ has at least two isomers. In general structure 4B, each cage structure, preferably adamantane, is bonded to three aromatic moieties that can participate in polymerization, wherein R _{1 to} R ₆ may be the same or different, and these two The cage structure is linked by aryl or substituted aryl. At least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ has at least two isomers. Preferably, at least two isomers of adamantane with respect to R ₇ are present.

When a monomer having a tetrahedral structure is used, the cage structure is a three-dimensional structure and is covalently bonded to four main chains. A representative monomer having a tetrahedral structure and its synthesis are shown in FIG. 3A. The monomer need not be limited to a compound having a substituted or unsubstituted adamantane as a cage structure, and may contain any cycloalkyl or cycloalkylene structure, cubane, substituted or unsubstituted diamantane, or fullerene as a cage structure Please note further. Substituents that are considered include alkyl, aryl, halogen, and functional groups. For example, adamantane, --CF3 group, tertiary alkyl group having 1-10 carbon atoms, a phenyl group, -COOH, -NO _2, or -F, may be substituted with -Cl or -Br, . Thus, depending on the chemistry of the cage structure, various groups other than the four aromatic moieties may be attached to the cage structure. For example, if it is desired to obtain a relatively low degree of crosslinking via a cage structure, 1 to 3 aromatic moieties can be combined with the cage structure, and the aromatic moiety is a reaction for crosslinking. It may or may not contain a sex group. If a higher degree of crosslinking is preferred, 4 or more aromatic moieties can be combined with the cage structure, and all or almost all of the aromatic moieties have one or more reactive groups. In addition, the aromatic moiety attached to the central cage structure may have other cage structures, which may be the same as or completely different from the central cage structure. Good. For example, the monomer considered may be a fullerene cage structure, in which case it may have a very large number of aromatic moieties and diamantane in the aromatic moieties. Thus, the considered cage structure can be covalently bonded to the first and second backbones and can be covalently bonded to more than two backbones.

  With respect to the chemical nature of the aromatic moiety, suitable aromatic moieties include phenyl groups, and more preferably include phenyl groups and reactive groups. For example, the aromatic moiety may comprise a tolan group, ie a (phenylethynylphenyl) group, or a substituted tolan, which is linked to the tolan by a carbon-carbon bond, such as a double bond, or a carbon-non-carbon atom bond. Another phenyl group may be included and may include an ethynyl group, an ether group, a keto group, or an ester group.

  Monomers having a pendant cage structure as illustrated in FIG. 7 are also considered, in which the diamantane group is used as the pendant group. However, the pendant cage structure is not limited to two diamantane structures. Alternative cage structures contemplated include chemically reasonable combinations of mono- and polysubstituted adamantane groups, diamantane groups, and fullerenes. Substituents can be introduced into a cage structure where specific solubility, oxidative stability, or other physicochemical properties are desired. Thus, the considered substituents include halogen, alkyl, aryl, and alkenyl groups, but also include functional and polar groups such as ester, acid groups, nitro and amino groups.

  It should also be understood that the main chain need not be homogeneous. In an aspect of another embodiment, if the low dielectric constant material includes first and second backbones having an aromatic moiety, a reactive group, and a cage compound attached to the backbone, the low dielectric constant Two or more chemically different backbones can be used to produce the rate material.

  With respect to reactive groups, many reactive groups other than ethynyl and tetracyclone groups can be used if the reactive group is crosslinkable with the first and second backbones without the use of an external crosslinker. it can. For example, a suitable reactive group includes benzocyclobutenyl. In another example, the first reactive group can include an electrophile and the second reactive group can include a nucleophile. In addition, the number of reactive groups includes (a) the reactivity of the first and second reactive groups, (b) the strength of the bridge between the first and second main chains, and (c) the low dielectric material. It depends greatly on the desired degree of cross-linking. For example, if there is steric hindrance in the first and second reactive groups (eg, an ethynyl group between two derivatized phenyl rings), a relatively large number of reactivities to bridge some of the two backbones Groups may be required. Similarly, when relatively weak bonds such as hydrogen bonds or ionic bonds are formed between reactive groups, a relatively large number of reactive groups may be required to form a stable bridge.

  If a reactive group in one main chain can react with the same type of reactive group in the other main chain, only one type of reactive group may be required. For example, ethynyl groups on two separate and homogeneous backbones can react in addition and cycloaddition reactions to form a crosslinked structure.

  It should also be understood that the number of reactive groups can also affect the ratio of intermolecular and intramolecular crosslinks. For example, when a relatively high concentration of reactive groups is present in the first and second main chains and both main chains are at a relatively low concentration, an intramolecular reaction tends to occur. Similarly, if there are relatively low concentrations of reactive groups in the first and second main chains and both main chains are at a relatively high concentration, intermolecular reactions are likely to occur. The balance between intramolecular reactions and intermolecular reactions can also be influenced by the distribution of heterogeneous reactive groups between the main chains. If an intermolecular reaction is desired, one type of reactive group may be present on the first main chain and another type of reactive group may be present on the second main chain. In addition, third and fourth reactive groups can also be used if continuous crosslinking is desired under different conditions (eg, two different temperatures).

  Preferred backbone reactive groups react by addition-type reactions, but many others such as nucleophilic and electrophilic substitution or elimination, radical reactions, etc., depending on the chemical nature of the other reactive groups. This reaction is also considered. Yet another reaction may include the formation of non-covalent bonds such as electrostatic bonds, ionic bonds, and hydrogen bonds. Thus, the first and second backbones can be cross-linked by covalent or non-covalent bonds formed between the same or different reactive groups that may be present on the same backbone or on two backbones. .

  In yet another aspect of another embodiment, if the cage structure has at least 8 atoms, the cage structure includes structures other than adamantane such as diamantane, bridged crown ether, cubane, or fullerene. Good. The selection of an appropriate cage structure is determined by the desired degree of steric demand of the cage structure. If a relatively small cage structure is preferred, one adamantane or diamantane group may be sufficient. Considered structures of the backbone with adamantane and diamantane groups are shown in FIGS. 8A and 8B. In the case of a large cage structure, fullerenes can be included. It should also be understood that another type of backbone need not be limited to one type of cage structure. It may include a suitable backbone, 2-5 cage structures, or other molecules, as well as different types of cage structures. For example, fullerenes can be added to one or both ends of the polymer backbone, and diamantane groups are located in other parts of the backbone. Furthermore, derivatized cage structures such as oligomerized and polymerized cage structures or multiple cage structures are also considered where a larger number of cage structures is desired. It should also be understood that the chemical composition of the cage structure need not be limited to carbon atoms, but may have atoms other than carbon atoms (ie, heteroatoms), and the heteroatoms considered are N, O , P, S, B and the like.

  With respect to the position of the cage structure, the cage structure can be bonded at various positions in the main chain. For example, when it is desirable to mask the terminal functional group of the main chain or to terminate the polymerization reaction to form the main chain, a cage structure can be used as the end cap. Representative structures of end caps are shown in FIGS. 9A and 9B. In other cases where a large number of cage structures are desirable, pendant structures where the cage structure is covalently bonded to the backbone are considered. The position of the covalent bond can vary and is highly dependent on the chemical properties that make up the backbone and cage structure. For example, a suitable covalent bond may involve a bridging molecule or functional group, and the other bond may be a single bond or a double bond. It is also specifically contemplated that when the cage group is a pendant group, more than one main chain can be attached to the cage structure. For example, one cage structure may be bonded to at least two or three or more main chains. Alternatively, it is also considered that the cage group can be part of the main chain.

  Referring now to FIG. 10, there is shown a representative polymer in which the first main group 10 and the second main group 20 are cross-linked by the first reactive group G15 and the second reactive group G25. A covalent bond 50 is formed by this cross-linking. Both backbones each have at least one aromatic moiety (not shown). The plurality of pendant cage structures 30 are covalently bonded to the first and second main chains, and the first main chain 10 further has a terminal cage group 32. The terminal cage group 32 and at least one pendant cage group 30 have at least one substituent R (40), and the substituent 40 may be a halogen, an alkyl group, or an aryl group. Each cage structure has at least 8 atoms.

(Adhesion promoter (b))
One of the adhesion promoters has the formula (R ₁₈ ) _f (R ₁₉ ) _g Si (R ₂₀ ) _h (R ₂₁ ) _i (wherein R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently , Hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl, wherein the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid group, or aryl, R ₁₈ , At least two of R ₁₉ , R ₂₀ , and R ₂₁ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid group, and f + g + h + i ≦ 4). Examples include H ₂ C═CHSi (CH ₃ ) ₂ H and H ₂ C═CHSi (R ₂₇ ) ₃ (wherein R ₂₇ is CH ₃ O, C ₂ H ₅ O, AcO, H ₂ C═CH , Or H ₂ C═C (CH ₃ ) O—) or a vinyl silane such as vinylphenylmethylsilane, the formula H ₂ C═CHCH ₂ —Si (OC ₂ H ₆ ) ₃ and H ₂ C═CHCH ₂ —Si (H) _{(OCH 3) 2} of allylsilanes, (3-glycidoxypropyl) glycidoxypropyl silane such as methyl diethoxy silane and (3-glycidoxypropyl) trimethoxysilane, formula _H 2 C = (CH _{3) COO (CH 2) 3} -Si (oR 28) 3 ( _{wherein, R 28} is alkyl, methacryloxypropyl silane preferably methyl or ethyl), _{2 N (CH 2) 3 Si} (OCH 2 CH 3) 3, H 2 N (CH 2) 3 Si (OH) 3 or _{H 2 N (CH 2) 3} OC (CH 3), 2 CH = CHSi (OCH ₃ ) Aminopropylsilane derivatives such as ₃ . The silane is commercially available from Gelest.

Another useful adhesion promoter is of the formula — [R ₂₂ C ₆ H ₂ (OH) (R ₂₃ )] _j —, where R ₂₂ is a substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or R ₂₃ is an alkyl, alkylene, vinylene, cycloalkylene, arylene, or aryl, where j = 3 to 100) phenol-formaldehyde resin or oligomer. 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 1500, which is commercially available from Schenectady International.

  Another useful adhesion promoter is a glycidyl ether such as, but not limited to, 1,1,1-tris- (hydroxyphenyl) ethane triglycidyl ether (which is commercially available from TriQuest). is there.

  Another useful adhesion promoter is an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group. Examples include trifunctional methacrylates, trifunctional acrylic esters, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and glycidyl methacrylate. All of the above are commercially available from Sartomer.

  Another useful adhesion promoter is a vinyl cyclic pyridine oligomer or polymer in which the cyclic group is pyridine, aromatic, or heteroaromatic.

  Useful examples include, but are not limited to, 2-vinyl pyridine and 4-vinyl pyridine, vinyl aromatics commercially available from Reilly, and, without limitation, vinyl quinoline, vinyl carbazole, vinyl imidazole. And vinyl heterocyclic aromatics such as vinyl oxazole.

  Preferably, the adhesion promoter (b) is a co-pending US patent application Ser. No. 09/471299, filed Dec. 23, 1999, assigned to the same assignee as the present application, the entire contents of which are hereby incorporated herein by reference. The polycarbosilane disclosed in US Pat. This polycarbosilane has the formula (I):

Wherein each of R ₈ , R ₁₄ , and R ₁₇ independently represents a substituted or unsubstituted alkylene, cycloalkylene, vinylene, arylene, or arylene, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom or an organic group containing alkyl, alkylene, vinyl, cycloalkyl, allyl, or aryl, which may be linear or branched, and R ₁₃ is organosilicon, Represents silanyl, siloxyl, or an organic group, a, b, c, and d satisfy the condition [4 ≦ a + b + c + d ≦ 100,000], and b, c, and d may all be 0, and each may be 0 In some cases). These organic groups can contain up to 18 carbon atoms, but usually 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 are those wherein R ₈ is substituted or unsubstituted alkylene or phenyl, R ₉ group is a hydrogen atom, and no other groups are present in the polycarbosilane chain, ie b, c And dihydridopolycarbosilane in which d is all 0. Another preferred class of polycarbosilanes where R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ , and R ₁₆ are substituted or unsubstituted alkenyl groups having from 2 to 10 carbon atoms. Polycarbosilane. An alkenyl group can be ethenyl, propenyl, allyl, butenyl, or any other unsaturated organic backbone having up to 10 carbon atoms. Alkenyl groups may have dienyl properties, including unsaturated alkenyl groups added or substituted on other alkyl or unsaturated organic polymer backbones. Examples of these preferred polycarbosilanes include dihydrido or alkenyl substituted polycarbosilanes such as polydihydridocarbosilane, polyallylhydridocarbosilane, and random copolymers of polydihydridocarbosilane and polyallylhydridocarbosilane.

In a more preferred polycarbosilane, the R ₉ group of formula I is a hydrogen atom, R ₈ is methylene, and the associated groups b, c, and d are 0. Other preferred polycarbosilane compounds of the invention are those wherein R ₉ and R ₁₅ are hydrogen, R ₈ and R ₁₇ are methylene, R ₁₆ is alkenyl, and the associated groups b and c are 0. Polycarbosilane of formula I. Polycarbosilanes can be prepared by methods known in the art and are also provided by manufacturers of polycarbosilane compositions. In the most preferred polycarbosilane, the R ₉ group of formula (I) is a hydrogen atom, R ₈ is —CH ₂ —, b, c, and d = 0, and a = 5-25. These most preferred polycarbosilanes are available from Starfire Systems, Inc. Specific examples of these most preferred polycarbosilanes are as follows.

As can be seen from formula (I), the polycarbosilane used in the present invention can have an oxidizing group in the form of a siloxyl group when c> 0. Thus, when c> 0, R ₁₃ represents an organosilicon, silanyl, siloxyl, or organic group. The oxidized form of polycarbosilane (c> 0) functions very efficiently in the present invention and is well within the scope of the present invention. Similarly, c may be 0 independently of a, b, and d, and the groups a, b, c, and d of the polycarbosilane of formula I may satisfy the condition [4 <a + b + c + d < 100,000] only, and both b and c may be 0, or may be 0 independently.

  The polycarbosilane of the present invention is preferably added in a small effective amount of about 0.5 wt.% Up to 20 wt.% Relative to the weight of the thermosetting composition (a) of the present invention. An amount of up to about 5.0% by weight is generally more preferred.

  Polycarbosilanes can also be produced by conventional polymerization methods using starting materials that are currently commercially available from many manufacturers. As examples of the synthesis of polycarbosilane, the starting material can be produced from a normal organosilane compound, or the polysilane is used as the starting material and the mixture of polysilane and polyborosiloxane is heated in an inert atmosphere. To produce the corresponding polymer, or heat the mixture of polysilane and low molecular weight carbosilane in an inert atmosphere to produce the corresponding polymer, or mix the mixture of polysilane and low molecular weight carbosilane in an inert atmosphere Heating in the presence of a catalyst such as diphenylsiloxane can produce the corresponding polymer. Polycarbosilanes can also be synthesized by the Grignard reaction reported in US Pat. No. 5,153,295, the description of which is incorporated herein.

  By mixing the preferred polycarbosilane with the thermosetting component (a) or polymer and exposing the composition to a heat source or high energy source, the resulting composition exhibits excellent adhesion across the polymer, and any coating Affinity is obtained at the contact surface. The polycarbosilane of the present invention also improves line control, viscosity, and film uniformity. The improvement of the line control can be confirmed by visual inspection.

  The compositions of the present invention may also contain additional components such as other adhesion promoters, antifoams, detergents, flame retardants, pigments, plasticizers, stabilizers, and surfactants.

(Usefulness)
The composition of the present invention comprising a thermosetting component (a) and an adhesion promoter (b) can obtain special results by mixing with other special additives. Representative examples of such additives include magnetic particles such as barium ferrite and iron oxide, possibly mixed with cobalt, or other metal-containing particles used in magnetic media, optical media, or other recording media, etc. Metal-containing compounds of: conductive particles such as metals and carbon used as conductive sealants, conductive adhesives, conductive coatings, electromagnetic interference (EMI) / radio frequency interference (RFI) shielding coatings, static dissipation, and It is an electrical contact. When these additives are used, the composition of the present invention acts as a binder. The compositions of the present invention are suitable for manufacturing, storage, or use environments such as metals, semiconductors, capacitors, inductors, conductors, solar cells, glass and glass fibers, quartz, and coatings to passivate the surfaces of quartz fibers. It can also be used for protection.

  The compositions of the present invention comprising a thermosetting component (a) and an adhesion promoter (b) are useful for seals and gaskets, preferably also around the scrim or alone as a seal or gasket layer. In addition, the compositions of the present invention can be used for antifouling coatings on objects such as boat parts, electrical switch sealants, bathtub and shower coatings, components of antifungal coatings, or flame retardant, light and moisture resistant. Is useful for imparting to a product. Because the compositions of the present invention are resistant to a range of temperatures, the compositions of the present invention are suitable for cold storage containers, autoclaves and ovens, as well as heat exchangers and other heated or cooled surfaces, and microwaves. It can be coated on an article exposed to.

  The composition of the present invention comprising a thermosetting component (a) and an adhesion promoter (b) is useful as a dielectric material. Preferably, the dielectric material of the present invention has a dielectric constant k of less than 3.0.

  The layer of the composition of the present invention comprising the thermosetting component (a) and the adhesion promoter (b) may be formed by solution methods such as spraying, roll coating, dip coating, spin coating, flow coating, or casting. Spin coating is preferred for microelectronic applications. Preferably, the composition of the present invention is dissolved in a solvent. Suitable solvents for use in such solutions of the compositions of the present invention include any suitable organic molecule, organometallic molecule, or pure substance or mixture of inorganic molecules that volatilizes at the desired temperature. Suitable solvents include aprotic solvents such as cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone, N-alkylpyrrolidinone (wherein the alkyl is about 1 to 4 carbon atoms). And aprotic solvents such as N-cyclohexylpyrrolidinone, and mixtures thereof. A wide variety of other organic solvents can be used in the present invention provided they can promote dissolution of the adhesion promoter and at the same time efficiently control the viscosity of the resulting solution as a coating solution. Various facilitating means such as stirring and / or heating may be used to promote dissolution. Other suitable solvents include methyl ethyl ketone, methyl isobutyl ketone, dibutyl ether, cyclic dimethylpolysiloxane, butyrolactone, γ-butyrolactone, 2-heptane, ethyl 3-ethoxypropionate, polyethylene glycol methyl ether, propylene glycol methyl ether acetate, Mention may be made of mesitylene, anisole, and hydrocarbon solvents such as xylene, benzene, and toluene. A preferred solvent is cyclohexanone. Usually the layer thickness is from 0.1 μm to about 15 μm. In the case of dielectric interlayers for microelectronics, the layer thickness is generally less than 2 μm.

  Preferably, the thermosetting component (a) and adhesion promoter (b) composition and solvent are treated at a temperature of about 30 ° C. to about 350 ° C. for about 0.5 hours to about 60 hours. In general, this treatment produces oligomers of thermosetting component (a) and adhesion promoter (b), which is confirmed by GPC.

  The compositions of the present invention can be used in electrical devices and more specifically as an intermediate layer in wiring associated with one integrated circuit (“IC”) chip. In general, an integrated circuit chip has a plurality of layers of the composition of the present invention and a plurality of layers of metal conductors on the surface. An integrated circuit chip may have regions of the composition of the present invention between separate metal conductors or between regions of the same layer or surface conductors of the integrated circuit.

  For IC applications of the polymer of the present invention, a solution of the composition of the present invention is applied to a semiconductor wafer using conventional wet coating methods such as spin coating, and other known methods such as spray coating and flow coating. The coating method can also be used in individual cases. By way of example, cyclohexanone of the composition of the present invention is spin coated onto a substrate having conductive elements formed therein, and then the coated substrate is heat treated. A typical formulation of the composition of the present invention adheres to a clean handling protocol to prevent contamination with trace metals in conventional equipment having a non-metallic lining, and the composition of the present invention is a cyclohexanone solvent. Prepared by dissolving. The resulting solution is preferably about 1% to about 50% by weight of thermosetting component (a) and adhesion promoter (b), and about 50% to about 99% by weight, based on the total solution weight. More preferably about 3 to about 20% by weight of thermosetting component (a) and adhesion promoter (b) and about 80% to about 97% by weight of solvent.

  Examples of use of the present invention are shown below. Formation of the layer by applying the composition of the present invention to a planar or certain shaped surface or substrate can be performed using any conventional apparatus, preferably a spin coater, for the reason used in the present invention. This is because the resulting composition has a controlled viscosity suitable for a coater or the like. The solvent can be evaporated using any suitable means such as simple air drying during spin coating, exposure to the ambient environment, or heating on a hot plate at up to 350 ° C. The substrate may have at least two layers of the inventive composition of thermosetting component (a) and adhesion promoter (b).

  Substrates contemplated by the present invention can include any desired substantially solid material. Particularly desirable substrate layers include films, glass, ceramics, plastics, metals or coated metals, or composite materials. In a preferred embodiment, the substrate is a silicon or germanium arsenide die or wafer surface, a package surface such as found in copper, silver, nickel, or gold plated lead frames, a circuit board or package interconnect pattern, a substrate A copper surface (such as “copper” is considered to include pure copper and copper oxide), such as found in interfaces via or via reinforced interfaces, polymer-based packaging or as found in polyimide-based flexible packages or Includes board interface, lead or other alloy solder ball surfaces, glass, and polymers. In a more preferred embodiment, the substrate comprises materials common in the packaging and circuit board industry, such as silicon, copper, glass, and polymers. The composition of the present invention can also be used as a dielectric substrate material for microchips, multichip modules, laminated circuit boards, or printed wiring boards. The circuit board comprised with the composition of this invention is mounted on the surface pattern of various electroconductive circuits. The circuit board may include various reinforcing materials such as non-conductive fiber fabric or glass cloth. Such a circuit board can be used on one side as well as on both sides.

The layer formed by the composition of the present invention has a low dielectric constant, high thermal stability, high mechanical strength, and furthermore, silicon, silicon nitride, silicon oxide, silicon oxycarbide, silicon dioxide, silicon carbide, silicon Excellent adhesion to electronic substrate surfaces such as oxynitride, titanium nitride, tantalum nitride, tungsten nitride, aluminum, copper, tantalum, organosiloxane, organosilicon glass, and fluorinated silicon glass. Because the adhesion promoter is molecularly dispersed, all attached surfaces including these layers, the underlying substrate, and the overlying capping or masking layer (eg, SiO ₂ and Si 3 N 4 capping layers, etc.) Excellent adhesion to. The use of these layers eliminates the need for further process steps in the form of application of at least one primer coating to adhere to the substrate of the film and / or the overlaid surface.

  After applying the composition of the present invention to the surface of the electronic substrate, the coated structure is subjected to a baking and heat curing step at an elevated temperature ranging from about 50 ° C. up to about 450 ° C. to cure the coating. The curing temperature is at least about 300 ° C. This is because lower temperatures are not sufficient to complete the reaction here. In general, curing is preferably performed at a temperature of about 375 ° C to about 425 ° C. Curing can be performed in a conventional curing chamber such as an electric furnace, hot plate, etc. and is generally performed in an inert (non-oxidizing) atmosphere (nitrogen) in the curing chamber. If effective to cure the organosilicon-modified thermosetting component (a) or polymer of the present invention to form the low-k dielectric layer of the present invention, any non-oxidizing or reducing atmosphere (e.g., Argon, helium, hydrogen, and nitrogen treatment gases) can be used to practice the present invention.

  Although not intended to be limiting, it is speculated that heat-treating the low dielectric constant composition of the present invention will form a crosslinked network structure of thermosetting component (a) and adhesion promoter (b). The Substantially, this heat treatment of the composition of the present invention converts the silane moiety of the preferred polycarbosilane adhesion promoter (b) to silylene / silyl groups, which in turn are the thermosetting component (a) and the substrate. It reacts with both unsaturated structures on the surface, thereby forming a chemical bond on the adhesive surface of the main thermosetting monomer (a), and the silylene / silyl group is present throughout the composition at any interface that is contacted by the chemical bond. Can be used for fastening and fixing. This reaction can occur during layer formation or during processing prior to layer formation. As mentioned above, the base of this invention is dispersed throughout the composition so that the layer of the present invention has excellent adhesion to both the underlying substrate surface and the surface overlying, such as a capping or masking layer. Show. An important point regarding the materials discovered in the present invention is the discovery that the preferred polycarbosilane adhesion promoters of Formula I have reactive hydride substituted silicon in the main chain structure of the polycarbosilane. This feature of the polycarbosilane allows (1) the thermosetting component (a) to be reactive and (2) a polycarbosilane modified thermosetting component (a) with improved adhesion.

  The resulting layer has a low dielectric constant k of 3.0 or less as defined herein. These layers exhibit excellent adhesion to a flat or certain cross-sectional semiconductor surface or substrate.

As described above, the polycarbosilane modified thermosetting component (a) or polymer coating of the present invention can function as an intermediate layer, and other dielectric (SiO ₂ ) coatings, SiO ₂ modified. Ceramic oxide layer, silicon containing coating, silicon carbon containing coating, silicon nitrogen containing coating, silicon-nitrogen-carbon containing coating, diamond-like carbon containing coating, titanium nitride, tantalum nitride, tungsten nitride, aluminum, copper, tantalum, organo Other coatings such as siloxane, organosilicon glass, and fluorinated silicon glass can also be covered. Such multilayer coatings are taught in US Pat. No. 4,973,526, the description of which is incorporated herein. And as fully explained, the polycarbosilane-modified thermosetting component (a) of the present invention prepared by the method of the present invention is formed between adjacent conductive paths on the manufactured electronic substrate or semiconductor substrate. It can be easily formed as a sandwiched dielectric layer.

The coating of the present invention can be used for copper dual damascene processing for integrated circuit manufacturing or metal (such as aluminum) removal processing. The compositions of the present invention are prepared by Michael E. Thomas due to (Thomas) "spin-laminated film of _{low-k eff} dielectric constant" _{(Spin-On Stacked Films for Low} k eff Dielectrics ", which is incorporated in Solid State Technology (7 May 2001) (the entire content of the description herein Can be used for any desired spin-on laminate film as taught in (1).

Example (Analytical Test Method)
Proton NMR: 2 to 5 mg of sample to be analyzed was placed in an NMR tube. About 0.7 ml of deuterated chloroform was added. The mixture was shaken by hand to dissolve the material. Samples were then analyzed using a Varian 400 MHz NMR.

  High Performance Liquid Chromatography (HPLC): An HPLC equipped with a Phenomenex luna Phenyl-Hexyl 250 × 4.6 mm 5 μm column was used. The column temperature was set to 40 ° C. Water and acetonitrile were used to improve peak separation.

The following experimental conditions were used.

Samples were prepared as follows.

  1,3,5,7-tetrakis (3 / 4-bromophenyl) adamantane and 1,3 / 4-bis [1 ′, 3 ′, 5′-tris (3 ″ / 4 ″ -bromophenyl) of Example 5 In the case of a mixture of halogenated intermediates such as a mixture of adamantyl] benzene, about 4% HCl (several ml) was added to the reaction mixture (0.5 ml to 1 ml) and shaken, water was added to the organic layer and shaken. An organic layer sample (20 μl) was taken and acetonitrile (1 ml) was added.

  1,3,5,7-tetrakis [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane of Example 5 and 1,3 / 4-bis {1 ′, 3 ′, 5′-tris [3 ”/ In the case of a mixture of final products such as a mixture of 4 ″-(phenylethynyl) phenyl] adamantyl} benzene, chloroform (5 ml) and 3-5% HCl (5 ml) are added to the reaction mixture (0.5 g) and mixed. , Shaken. The organic layer was washed with water. An organic layer sample (100 μl) was added to tetrahydrofuran (0.9 ml).

  Gel Permeation Chromatography (GPC): GPC analysis was performed using a Water 717 plus Autosampler, a Waters in-line degasser, a Waters 515 HPLC pump, a Waters 410 differential refractometer. (Waters 410 Differential Refractometer) (Rl detector), and a Waters liquid chromatography system consisting of two columns HP PI gel 5μ MIXED D. The analysis conditions are as follows.

A sample (10 mg) was prepared by adding to tetrahydrofuran (1 ml).

  Mass Spectrometry (MS): This analysis was performed using a Hewlett-Packard Series 1050 HPLC system as a chromatography inlet and a Finnigan with an Atmospheric Pressure Ionization (API) interface unit. ) / MAT TSQ7000 triple stage quadrupole mass spectrometer. Both mass spectrometric ion current and variable single wavelength UV data were determined as time-intensity chromatograms.

  Chromatography was performed on a Phenomenex Luna 5 micron phenyl hexyl column (250 x 4.6 mm). Sample auto-injection was usually 10 μl or 20 μl concentrated solution, both with and without tetrahydrofuran. Mobile phase flow through the column is 1.0 ml / min acetonitrile / water, programmed to be 70/30 for the first 5 minutes, and then 100% acetonitrile in 15 minutes and maintained for up to 100 minutes. (Longer than actually required for complete elution of 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 μA, about 5 kV for positive ionization and about 4 kV for negative ionization. The heated capillary line was maintained at 200 ° C and the vaporizer cell was maintained at 400 ° C. The detection system after quadrupole mass spectrometry was set to a conversion dynode 15 kV and an electron multiplier voltage 1500 V. Typically, the mass spectrum is approximately 0.5 / sec and in the positive ionization mode approximately m / z 150-2000 a. m. u. In the negative ionization mode, m / z 125-2000a. m. u. Scanned.

  Differential Scanning Calorimetry (DSC): DSC measurements were performed using a controller and associated software on a TA Instruments 2920 Differential Scanning Calorimeter. Analysis was performed using a standard DSC cell in the temperature range 250 ° C. to 725 ° C. (inert atmosphere: nitrogen 50 ml / min). Liquid nitrogen was used as the cooling gas source. A small sample (10-12 mg) was carefully weighed into an automated DSC aluminum sample pan (part number 990999-901) using a Mettler Toledo Analytical balance with an accuracy of ± 0.0001 g. The sample was sealed by covering the pan with a lid that had been previously punctured. The sample was heated from 0 ° C. to 450 ° C. at a rate of 100 ° C./min in a nitrogen atmosphere (cycle 1) and then cooled to 0 ° C. at a rate of 100 ° C./min. A second cycle was performed immediately, increasing from 0 ° C. to 450 ° C. at a rate of 100 ° C./min (repeating cycle 1). The crosslinking temperature was determined from the first cycle.

  FTIR analysis: FTIR spectra were measured using a Nicolet Magna 550 FTIR (Nicolet Magna 550 FTIR) spectrometer in transmission mode. The background spectrum of the substrate was measured using an uncoated substrate. The spectrum of the film was measured using the substrate as background. Next, the spectrum of the film was analyzed and converted into a peak position and intensity.

  Dielectric constant: A thin film of aluminum was coated on the hardened layer, capacitance-voltage measurement was performed at 1 MHz, and the dielectric constant was determined by calculating the k value based on the thickness of the layer.

  Glass transition temperature (Tg): The glass transition temperature of the thin film was determined by measuring the thin film stress as a function of temperature. Thin film stress measurements were performed with a KLA 3220 Flexus. Prior to film measurement, the uncoated wafer was annealed at 500 ° C. for 60 minutes to avoid errors due to stress relaxation of the wafer itself. The material to be tested was then deposited on the wafer and all necessary process steps were performed. Subsequently, the wafer was attached to a stress gauge and the wafer bow as a function of temperature was measured. If the wafer thickness and film thickness were known, a stress vs. temperature graph was created by instrument calculations. The results were displayed in the form of a graph. In order to determine the Tg value, a horizontal tangent line was drawn (slope was 0 in the stress vs. temperature graph). The Tg value was the value at the intersection of the graph and the horizontal tangent.

  Since the measurement process itself can affect Tg, it should be recorded whether the Tg was determined after the first temperature cycle or after the cycle after the maximum temperature was used.

  Isothermal gravimetric analysis (ITGA) Weight loss: Total weight loss was measured using a TA Instruments 2950 Thermogravimetric Analyzer (TGA) on a TA Instruments 2950 Thermogravimetric Analyzer (TGA). . A Platinel II Thermocouple and a standard furnace were used at a temperature range of 25 ° C. to 1000 ° C. and a heating rate of 0.1 ° C. to 100 ° C./min. A small sample (7-12 mg) was weighed with a TGA balance (resolution: 0.1 g, accuracy: ± 0.1%) and heated in a platinum pan. The sample was heated under a nitrogen atmosphere with a purge rate of 100 ml / min (60 ml / min is fed to the heating furnace and 40 ml / min is shared with the balance). The sample was equilibrated at 20 ° C. for 20 minutes under a nitrogen atmosphere, then the temperature was increased to 200 ° C. at 10 ° C./min and maintained at 200 ° C. for 10 minutes. The temperature was then increased to 425 ° C. at a rate of 10 ° C./min and maintained at 425 ° C. for 4 hours. The weight loss after 4 hours at 425 ° C. was calculated.

  Shrinkage: Film shrinkage was measured by measuring film thickness before and after treatment. Shrinkage was expressed as a percentage of the original film thickness. Shrinkage was positive when the film thickness decreased. The actual thickness measurement is described in J.H. A. Optically performed using a Worlam M-88 (JA Woollam M-88) spectroscopic ellipsometer. Optimum values of ψ and δ were calculated using the Cauchy model (for details on ellipsometry, see, eg, HG Thomkins and William A. McGahan, “ Spectral Ellipsometry and Reflection Measurement "(Spectroscopic Ellipsometry and Reflectometry), John Wiley and Sons, Inc., 1999).

  Refractive index: The refractive index measurement is described in A. Performed simultaneously with thickness measurement using a Warram M-88 spectroscopic ellipsometer. The optimal values of ψ and δ were calculated using Cauchy's model. Unless otherwise stated, the refractive index is reported at a wavelength of 633 nm (for details on ellipsometry, see eg HG Spectral Ellipsometry and Reflection Measurement, edited by HG Tomkins and William A. Magahan, (John Wiley and Sons, 1999).

  Elastic modulus and hardness: Elastic modulus and hardness were measured by an indentation test of the device. Measurements were made using MTS Nanoindenter XP (MTS Systems Corp., Oak Ridge, TN). In particular, a continuous stiffness measurement method has been used, which makes it possible to measure elastic modulus and hardness accurately and continuously rather than measuring discontinuous values from no-load curves. The system was calibrated using fused silica with a nominal elastic modulus of 72 ± 3.5 GPa. The elastic modulus of the fused silica was determined from the average value between the indentation depths of 500 nm and 1000 nm. For thin films, the modulus and hardness values were roughly determined from the curve of minimum modulus vs. depth, and the depth was usually 5% to 15% of the film thickness.

  Tape test: The tape test was performed according to the standard of ASTM D3359-95. A grid was cut into the dielectric layer as follows. The tape test was performed along a grid cut by the method described later. (1) Place the adhesive tape (preferably Scotch brand # 3m600-1 / 2X1296) on the layer of the present invention and press firmly to make sufficient contact, (2) against the layer surface The tape was quickly peeled off at an angle of 180 °. A sample is considered acceptable if the layer remains intact on the wafer, and is rejected if any or all of the film is peeled off by the tape.

  Stud sampling test: Epoxy coated studs were attached to the wafer surface with the layer of the present invention. In order to prevent excessive stress concentration on the substrate warp and stud end, a ceramic backing plate was attached to the back surface of the wafer. Studs were pulled vertically from the wafer surface by a test apparatus using standard sampling procedures. The stress applied until failure and the position of the interface were recorded.

  Compatibility with solvent: Compatibility with solvent was investigated by measuring film thickness, refractive index, FTIR spectrum, and dielectric constant before and after solvent treatment. In the case of compatible solvents, no significant difference is observed.

Example 1
(Synthesis of 4,6-bis (adamantyl) resorcinol)
To a 250 mL three-necked flask equipped with a nitrogen inlet, thermocouple, and condenser was added resorcinol (11.00 g, 100.0 mmol), bromoadamantane (44.02 g, 205.1 mmol) and toluene (150 mL). When this mixture was heated to 110 ° C., a clear solution was obtained. After the reaction was continued for 48 hours, TLC was performed and it was found that all resorcinol was gone. The solvent was removed and the solid was crystallized from hexane (150 mL). The disubstituted product was obtained as a white solid in 66.8% yield (25.26 g). An additional 5.10 g of product was obtained by concentrating the mother liquor remaining after the first recovery and performing silica gel column chromatography. The overall yield of product was 80.3%. The product was characterized by proton NMR, HPLC, FTIR, and MS.

(Polyarylene ether of 4,6-bis (adamantyl) resorcinol) polymerization to main chain)
A 250 mL three-necked flask equipped with a nitrogen inlet, thermocouple, and Dean-Stark trap was charged with bis (adamantyl) resorcinol (7.024 g, 18.57 mmol), FBZT (5.907 g, 18. 57 mmol), potassium carbonate (5.203 g, 36.89 mmol), DMAC (50 mL), and toluene (25 mL) were added. The reaction mixture was heated to 135 ° C. to obtain a clear solution. The reaction was continued at this temperature for 1 hour, after which part of the toluene was removed and the temperature was raised to 165 ° C. The polymerization process was monitored by GPC. The reaction was stopped when M _w = 22,000. An additional 50 mL of DMAC was added to the reaction flask. The obtained solid was filtered at room temperature, extracted with hot dichloromethane (150 mL × 2), methanol (150 ml) was added to the solution to precipitate a white solid, and this was collected by filtration. The yield was 65.8% (8.511 g). This solid was dissolved in tetrahydrofuran (150 mL), and methanol (300 mL) was slowly added to the resulting solution. The precipitated white solid was collected by filtration and dried at 90 ° C. under reduced pressure.

Example 1A
A composition was prepared from the product of Example 1, a silane adhesion promoter, and a solvent and spin coated onto a substrate.

Example 2
(Synthesis of another polymer)

  The synthetic procedure described in Example 1 was used, except that 4,4'-difluorotolane was used as the difluoro compound.

  Example 2A

  The synthetic procedure of Example 1 was followed except that 3,4-difluorotetraphenylcyclodienone was used as the difluoro compound.

Example 2B
A composition was prepared from the product of Example 2, a phenol-formaldehyde resin adhesion promoter, and a solvent and spin coated onto a substrate.

Example 2C
A composition was prepared from the product of Example 2A, a glycidyl ether adhesion promoter, and a solvent and spin coated onto a substrate.

Example 3
(Another main chain considered)
The following structures are representative backbones considered that can be generated according to the general synthetic procedures of Examples 1 and 2.

Example 3A
A composition was prepared from the first polymer of Example 3, an unsaturated carboxylic acid ester adhesion promoter, and a solvent and spin coated onto a substrate.

Example 3B
A composition was prepared from the second polymer of Example 3, a vinyl pyridine oligomer or polymer adhesion promoter, and a solvent and spin coated onto a substrate.

Example 3C
A composition was prepared from the third polymer of Example 3, a vinyl aromatic oligomer or polymer adhesion promoter, and a solvent and spin coated onto a substrate.

Example 3D
A composition was prepared from the fourth polymer of Example 3, a vinyl heteroaromatic oligomer or polymer adhesion promoter, and a solvent and spin coated onto a substrate.

Example 4
Monomers endcapped with adamantanyl as shown in FIGS. M.M. Lewis, L.L. J. et al. Mathias, N .; Synthesized as described in Wiegal, ACS Polymer Preprints, 36 (2), 140 (1995).

Example 4A
A composition was prepared from the product of Example 4, a vinyl silane adhesion promoter, and a solvent and spin coated onto a substrate.

Example 5
This example demonstrates the preparation of a thermosetting component (a).

  (Step 1: Synthesis of 1,3,5,7-tetrabromoadamantane (TBA))

  The synthesis of 1,3,5,7-tetrabromoadamantane started from commercially available adamantane, G. P. Sollott and E.I. E. Gilbert, J.M. Org. Chem. 45, 5405-5408 (1980), B.I. Scheltel, V.M. Stampflin, J.A. Wendling, J.M. H. Wendorff, W.M. Heights, and R.A. Neuhaus, Colloid Polym. Sci. , 274, 911-919 (1996), or A.M. P. Khardin, I.D. A. Novakov, and S.N. S. Radchenko, Zh. Org. Chem. , 9, 435 (1972). Synthesized periodically in amounts up to 150 g per batch.

(Step 2: 1,3,5,7-tetrakis (3 / 4-bromophenyl) adamantane (TBPA) and 1,3 / 4-bis [1 ′, 3 ′, 5′-tris (3 ″ / 4 ″) -Bromophenyl) adamantyl] benzene (BTBPAB) mixture)
In the first step, TBA is reacted with bromobenzene and 1,3.5,7-tetrakis (3 / 4-bromo) as described in Macromolecules, 27, 7015-7023 (1994) (supra). From the HPLC-MS analysis where phenyl) adamantane (TBPA) appears to be formed, of the total reaction product, about 50% of the desired TBPA is present, 40% tribrominated tetraphenyladamantane and about 10% dibromination. It was found to be accompanied by tetraphenyladamantane.

  Specifically, the experimental procedure in Step 2 is performed as follows. A dried 5 L three-necked round bottom flask, water condenser, magnetic stir bar, heating mantle, thermocouple, thermal controller, and outlet to N2 inlet-30% KOH solution were assembled. The flask was purged with N2 for 10 minutes, 2 L (62% v / v of total volume) of bromobenzene was placed in the flask and the stir bar was moved. TBA (160.00 ± 0.30 g) was added and the used funnel was washed with 1 L (31% v / v of total volume) bromobenzene. An HPLC sample of the starting material was taken and compared to a standard HPLC chromatogram. Aluminum bromide (32.25 ± 0.30 g) was added to the solution and the funnel was washed with 220 mL (7% v / v of total volume) bromobenzene. At this point, the solution was deep purple and no precipitate was seen. The reaction mixture was stirred at room temperature for 1 hour. After 1 hour, the temperature of the reaction mixture was raised to 40 ° C. The temperature was raised to 40 ° C. and the reaction mixture was stirred for 3 hours. Each HPLC sample was taken at 40 ° C. at 1 hour + 3.0 hours. The reaction was terminated when no trace of TBA was seen in the HPLC chromatogram. After completion of the reaction, the dark reaction mixture was diluted with 7 L (217% v / v bromobenzene total volume) deionized water, 2 L (62% v / v bromobenzene total volume) ice, And a 20 L reactor containing 300 mL (37%) HCl (9% v / v relative to the total volume of bromobenzene). The reaction mixture was stirred vigorously for 1 hour ± 10 minutes using an overhead stirrer.

  The organic layer was transferred to a separation chamber and washed twice with 700 ml (22% v / v with respect to the total volume of bromobenzene) of deionized water. Place the washed organic layer into a 4 L separatory funnel and slowly place the organic layer of the separatory funnel into 16 L (5 times the total volume of bromobenzene) methanol in a 30 L reactor placed under an overhead stirrer. The solid was allowed to settle for 25 minutes ± 5 minutes. After the addition was complete, the methanol suspension was stirred vigorously for 1 hour ± 10 minutes. The methanol suspension was suction filtered through a Buchner funnel (185 mm). The solid obtained on the filter cake was washed with 600 mL (19% v / v based on the total volume of bromobenzene) methanol three times. The obtained solid was dried under reduced pressure for 30 minutes.

  The obtained pink powder was transferred to a crystal dish with a spatula, placed in a vacuum oven, dried overnight, and weighed after drying. The powder was re-dried in a vacuum oven for an additional 2 hours until the weight change was <1% and reweighed. After drying the solid, the final weight was recorded and the yield was calculated. The product was about 50% TBPA, 40% tribrominated tetraphenyladamantane, and 10% dibrominated tetraphenyladamantane as described above. The yield was 176.75g. 3-5 wt% BTBPAB was produced.

(Step 3: Synthesis of TBPA and BTBPAB)

Unexpectedly, reaction of the aforementioned product mixture with new reagents and catalysts (bromobenzene and AlCl ₃ , 1 min at 20 ° C.) resulted in tetrabrominated, tribrominated, and dibrominated monomers The ratio of TBPA in this mixture increased from about 50% to about 90-95%. BTBPAB remained at 3-5% by weight. The inventors have confirmed several times and confirmed the surprising result that this method is a new method for converting the precursor mixture into the thermosetting component (a), as described below and shown in FIG. They got.

  Specifically, the experimental procedure of step 3 is as follows. The equipment used was the same as in step 2 above.

  The corresponding required amounts of bromobenzene and aluminum bromide were calculated based on the yield of TBPA synthesized in the previous or conventional synthesis. An appropriate amount (80% v / v of the total volume) of bromobenzene was placed in the flask and the stir bar was moved. The total amount of TBPA synthesized in step 2 above was added and the funnel used was washed with an appropriate amount (10% v / v of total volume) of bromobenzene. An HPLC sample of the starting material was taken and compared to a standard HPLC chromatogram. The entire amount of aluminum bromide was added to the solution and the used funnel was washed with the remaining (10% of the total volume) bromobenzene. At this point, the solution was deep purple and no precipitate was seen. The reaction mixture was stirred at room temperature for 17 minutes. HPLC samples were taken after 5 and 17 minutes. The reaction was terminated when the peak corresponding to TBPA became dominant in the HPLC chromatogram. After completion of the reaction, the dark reaction mixture was diluted with 7 L (217% v / v bromobenzene total volume) deionized water, 2 L (62% v / v bromobenzene total volume) ice, And a 20 L reactor containing 300 mL (37%) HCl (9% v / v relative to the total volume of bromobenzene) and stirred vigorously using an overhead stirrer for 1 hour ± 10 minutes.

  The organic layer is transferred to a separatory funnel and washed twice with 700 ml (22% v / v of total volume of bromobenzene) with deionized water and 700 ml (22% v / v of total volume of bromobenzene). Was washed 3 times with a saturated NaCl solution. Put the washed organic layer into a 4 L separatory funnel and put the organic layer of the separatory funnel into the appropriate amount (5 times the total volume of bromobenzene) methanol in a 30 L reactor placed under an overhead stirrer. Slowly added and allowed to settle for 25 minutes ± 5 minutes. After the addition was complete, the methanol suspension was stirred vigorously for 1 hour ± 10 minutes. The methanol suspension was suction filtered with a Buchner funnel (185 mm). The solid obtained on the filter cake was washed with 600 mL (19% v / v based on the total volume of bromobenzene) methanol three times. The obtained solid was dried under reduced pressure for 30 minutes.

  The resulting pink powder is transferred to a crystallization dish with a spatula, placed in a vacuum oven, dried overnight, weighed after drying, re-dried in a vacuum oven for an additional 2 hours until the weight change is <1%, and reweighed Went. After drying the solid, the final weight was recorded and the yield was calculated. The yield was 85%.

  (Step 4: 1,3,5,7-tetrakis [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane (TPEPA) and 1,3 / 4-bis {1 ′, 3 ′, 5′-tris [ Synthesis of a mixture of 3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene (BTPEPAB)

  Following the general reaction protocol for Heck's ethinylation using a palladium catalyst, a mixture of TBPA and BTBPAB is reacted with phenylacetylene to yield 95% to 97% by weight of 1,3,5,7-tetrakis of the final product. [3 ′ / 4 ′-(Phenylethynyl) phenyl] adamantane (TPEPA) is formed as an isomer mixture and an additional 3-5 wt% 1,3 / 4-bis {1 ′, 3 ′, 5′-tris [3 "/ 4"-(Phenylethynyl) phenyl] adamantyl} benzene (BTPEPAB) was formed as a mixture of meta and para isomers (identified by GPC, NMR, and HPLC). The mixture of TPEPA and BTPEPAB produced in the reaction containing TBPA is soluble in cyclohexanone.

  Specifically, the experimental procedure of Step 4 is as follows. Assemble a dry 2L three-necked round bottom flask, water cooler, overhead stirrer, heating mantle, thermocouple, thermal controller, dropping funnel, two-neck adapter, and outlet to N2 inlet-30% KOH solution It was. The flask was purged with N2 for 10 minutes.

  The mixture of TBPA and BTBPAB obtained by the synthesis procedure of Step 3 above was weighed. Triethylamine (TEA) (total calculated TEA volume—300 mL) was added to the reaction flask, the overhead stirrer was turned on, and the following compounds were added in the order listed. Dichlorobis (triphenylphosphine) palladium [II] catalyst addition, wash with 50 mL of used funnel (4% of total volume) TEA and stir for 5 min, add triphenylphosphine, add 50 mL of funnel (4% of total volume) Wash with TEA and stir for 5 minutes, add copper (I) iodide, wash the funnel with 50 mL (4% of total volume) TEA and stir for 5 minutes. The total amount of TBPA obtained in the synthesis of Step 3 above was added and the funnel used was washed with 100 mL (8% of the total volume) of TEA. The flask was heated to 80 ° C. An analytical HPLC sample was taken after the reaction mixture temperature reached 80 ° C. This was the starting material.

  The amount of phenylacetylene whose amount was measured was diluted with 50 mL (4% of the total volume) of TEA was placed in a dropping funnel, and one of the two-neck adapter ports was attached. Diluted phenylacetylene was added dropwise to the reaction mixture over 30 minutes ± 10 minutes. This was an exothermic reaction. The temperature was controlled using a water bath. Heating was continued for 3 hours. After heating at 80 ° C. for 3 hours, the reaction was stopped. An HPLC sample was taken at 3 hours at 80 ° C.

  The reaction mixture was cooled to 50 ° C. and filtered through a Buchner funnel (185 mm). The resulting crude solid was washed twice with 600 mL TEA (v / v% = 52% with respect to the calculated TEA volume). The filter cake was put into a 4 L beaker, 1 L (v / v% = 87% based on the calculated TEA volume) of TEA was added to the contents, and the mixture was stirred at room temperature for 15 minutes. The resulting filter cake was filtered through a Buchner funnel (185 mm) and the resulting crude solid was washed with 300 mL TEA (v / v% = 26% based on calculated TEA volume). The obtained solid was dried under reduced pressure overnight, and HPLC, DSC, trace metal, and UV-VIS analysis were performed on 3 g of the crude product sample.

  The differences in interpretation between the prior art and the present invention are as follows. FIGS. 11 and 12 show the preparation of the isomers described below, and the Roman numerals in this example correspond to the Roman numerals in FIGS. As explained in the “Background” section, Reichert's goal is to prepare 1,3,5,7-tetrakis [(4-phenylethynyl) phenyl)] adamantane of the defined structure, ie this compound Was to prepare one p-isomer of 1,3,5,7-tetrakis [4 ′-(phenylethynyl) phenyl] adamantane (VIII). This sole compound with a defined structure (which can be characterized by analytical methods) was the goal of Reichert's research.

Reichert's plan is shown in the following diagram:
1,3,5,7-tetrabromoadamantane (I) → 1,3,5,7-tetrakis (4′-bromophenyl) adamantane (II) (p-isomer) → 1,3,5,7- Tetrakis [4 ′-(phenylethynyl) phenyl)] adamantane (VIII) (p-isomer)
Reichert is a mixture of isomers of 1,3,5,7-tetrakis (bromophenyl) adamantane containing a combination of p- and m-bromophenyl groups attached to an adamantane core (see below). Since it was thought that 7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III) was synthesized, it failed in step (I) → (II), and it was thought that the target could not be achieved. As an indication of this, Reichert states that “there is no regioselectivity during arylation, so the Friedel-Crafts reaction on adamantane cannot be carried out and is easily generated, 1,3,5,7-tetraphenyl. It was decided to proceed with further research on the derivatization of adamantane (VI). " In order to synthesize one p-isomer, 1,3,5,7-tetrakis [4 ′-(phenylethynyl) phenyl)] adamantane (VIII), Reichert
1,3,5,7-tetraphenyladamantane (VI) → 1,3,5,7-tetrakis (4′-iodophenyl) adamantane (VII) → 1,3,5,7-tetrakis [4 ′-( Phenylethynyl) phenyl] adamantane (VIII)
I planned a "detour procedure" like

Reichert continued this route and isolated a single p-isomer (VIII), but the compound was found to be poorly soluble and Reichert was able to obtain a ¹³ C NMR spectrum of the compound. There wasn't. Reichert found that “Compound 3 [(VIII)] was sufficiently soluble in chloroform to take a ¹ H NMR spectrum. However, a capture time was practical to obtain a ¹³ C NMR spectrum of the solution. "The product was identified using solid-state NMR," says Reichert's dissertation (described above). To confirm these results, Reichert's compounds were tested in several standard organic solvents and found to be substantially insoluble in all tested organic solvents.

  Thus, in other words, what Reichert thought was prepared was 1,3,5,7-tetrakis (3 '/ 4'-bromophenyl) adamantane (III), but could not continue in this direction. Because this product was not a single isomer of defined structure. Reichert did not prepare one para isomer, 1,3,5,7-tetrakis (4′-iodophenyl) adamantane (VII), but it did not produce one isomeric 1,3,5, It was changed to 7-tetrakis [4 ′-(phenylethynyl) phenyl] adamantane (VIII), which was found to be insoluble and therefore not useful.

  The inventors of the present invention repeated a large number of reactions of 1,3,5,7-tetrabromoadamantane and bromobenzene, and the present inventors obtained a reaction product of 1,3,5,7-tetrabromoadamantane and bromobenzene. Analysis revealed that 1,3,5,7-tetrakis (3 ′ / 4′-), not 1,3,5,7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III) (Reichert's reference). It was found to be a mixture of bromophenyl) adamantane (III) with approximately the same amount of 1-phenyl-3,5,7-tris (3 ′ / 4′-bromophenyl) adamantane (IV). This conclusion was confirmed by LC-MS analysis and elemental analysis.

The present inventors have been able to find the cause of such a reaction pathway. Bromobenzene is known to substantially imbalance the conditions of the Friedel-Crafts reaction (GA Olah, WS Tolgiesi, REEA. Dear, J. Org. Chem., 27, 3441-3449 (1962)):
2PhBr → PhH + Br ₂ Φ
As the concentration of benzene in the reaction mixture increases, substitution of bromine [I] [or bromophenyl of (III)] occurs, and due to the high proportion of benzene, equilibrium is reached quickly and approximately the same amount of (III) And (IV) are generated.

  Therefore, Reichert did not synthesize 1,3,5,7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III) (as he had thought), Almost 1: 1 of 5,7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III) and 1-phenyl-3,5,7-tris (3 ′ / 4′-bromophenyl) adamantane (IV) Was synthesized.

  In order to move the equilibrium to the 1,3,5,7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III) side, we have 1,3,5,7-tetrabromoadamantane and A solid reaction product of bromobenzene [1,3,5,7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III) and 1-phenyl-3,5,7-tris (3 ′ / 4′- Bromophenyl) adamantane (IV) 1: 1 mixture] was treated with fresh bromobenzene in the presence of aluminum bromide. It was found that the phenyl group of 1-phenyl-3,5,7-tris (3 ′ / 4′-bromophenyl) adamantane (IV) was immediately replaced with pure bromobenzene, so formation in solution for 30 seconds The product contained about 90-95% 1,3,5,7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III). This situation is observed at room temperature for about 5-10 minutes, after which the benzene concentration slowly increases, thereby causing 1-phenyl-3,5,7-tris (3 ′ / 4′-bromophenyl) adamantane (IV) concentration Increased, and after a few hours, equilibrium was reached again and 1,3,5,7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III) and 1-phenyl-3,5,7-tris ( The concentration of 3 ′ / 4′-bromophenyl) adamantane (iv) became almost the same.

  Thus, 1,3,5,7-tetrakis (3 ′ / 4′-bromophenyl) adamantane (III) (considered by Reichert) was synthesized in the presence of aluminum bromide. -Tetrabromoadamantane can be prepared by performing a second treatment of the solid reaction product of bromobenzene.

  When a Heck reaction between 1,3,5,7-tetra (3 ′ / 4′-bromophenyl) adamantane (III) and phenylacetylene is performed, 95% to 97% by weight of 1,3,5,7- Tetra [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane (V) (a mixture of p- and w-isomers formed. (1) Para, para, para, para, (2) para, Para, para, meta, (3) para, para, meta, meta, (4) para, meta, meta, meta, and (5) meta, meta, meta, meta, and five isomers were generated. Trace amounts of o-isomers may also be present) and 3-5% by weight of 1,3 / 4-bis {1 ′, 3 ′, 5′-tris [3 ″ / 4 ″ -phenylethynyl) phenyl] adamantyl } A new mixture with benzene (14 isomers formed) was obtained. These were identified by GPC, NMR, and HPLC and were very soluble in toluene, xylene, cyclohexanone, anisole, propylene glycol methyl ether acetate, mesitylene, cyclohexyl acetate. For example, the solubility in cyclohexanone is> 20%. This property makes it possible to spin coat and this material can be used practically in the field of layered materials and semiconductors, particularly preferably.

  Therefore, from the intermediate 1,3,5,7-tetra (3 ′ / 4′-bromophenyl) adamantane (III) prepared by the inventors, 1,3,5,7-tetra [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane (V) and 1,3 / 4-bis {1 ′, 3 ′, 5′-tris [3 ″ / 4 ″-(phenylethynyl) phenyl] adamantyl} benzene (p -A soluble mixture of isomers and m-isomers), which is useful as the thermosetting component (a).

Example 6
This example shows the preparation of another thermosetting monomer (a).

  (Step 1: Synthesis of m- and p-bromotolane isomers)

  A 500 mL three-necked round bottom flask equipped with an addition funnel and a nitrogen gas inlet was charged with 4-iodobromobenzene (25.01 g, 88.37 mmol), triethylamine (300 mL), bis (triphenylphosphine) palladium [II] chloride ( 0.82 g), and copper iodide [I] (0.54 g) were added. Subsequently, a solution of phenylacetylene (9.025 g, 88.37 mmol) in triethylamine (50 mL) was added slowly and the temperature of the solution was maintained below 35 ° C. with stirring. The mixture was stirred for an additional 4 hours after the end of the addition. The solvent was evaporated on a rotary evaporator and 200 mL of water was added to the residue. The product was extracted with dichloromethane (2 × 150 mL). These organic layers were mixed and the solvent was removed with a rotary evaporator. The residue was washed with 80 mL hexane and filtered. HPLC showed a pure product (yield 19.5 g, 86%). Further purification was performed by chromatography on a silica short column (eluent is a 1: 2 mixture of toluene and hexane). A white crystalline solid was obtained after removal of the solvent. The purity of this product was examined by GC / MS in acetone solution and further characterized by proton NMR.

  (Step 2: Synthesis of m- and p-ethynyltolane)

  The synthesis of p-ethynyltolane from p-bromotolane was performed in two steps. In the first stage, trimethylsilylacetylene (TMSA, supra) is used to perform trimethylsilylethynylation of p-bromotolane, and in the second stage, the reaction product of the first stage is converted to the final target product. It was.

  Step a (trimethylsilylethynyl of 4-bromotolane): 4-bromotolane (10.285 g) in a 5 liter four-necked round bottom flask equipped with an overhead magnetic stirrer and condenser and placed in an N2 purged heating mantle. 40.0 mmol), ethynyltrimethylsilane (5.894 g, 60.0 mmol), 0.505 g (0.73 mmol) dichlorobis (triphenylphosphine) palladium [II] catalyst, 40 mL anhydrous triethylamine, 0.214 g (1 .12 mmol) of copper iodide [I] and 0.378 g (1.44 mmol) of triphenylphosphine. The mixture was heated to gentle reflux (about 88 ° C.) and maintained at reflux for 1.5 hours. The reaction mixture became a viscous black paste and was subsequently cooled. Thin layer chromatographic analysis showed that the starting 4-bromotolane was completely converted to one product. The solid was filtered, washed with 50 mL triethylamine, mixed with 400 mL water and stirred for 30 minutes. The solid was filtered and washed with 40 mL methanol. The resulting crude solid was recrystallized from c500 mL of methanol. On standing, shiny silver crystals precipitated. These were isolated by filtration and washed twice with 50 mL of methanol. 4.662 g was recovered (yield 42.5%).

  Step b (Conversion of 4- (trimethylsilyl) ethynyltolan to 4-ethynyltolane): To a 1 liter three-necked round bottom flask fitted with a nitrogen inlet and overhead magnetic stirrer, 800 mL of absolute methanol, 12. 68 g (46.2 mmol) of 4- (trimethylsilyl) ethynyltolan and 1.12 g of anhydrous potassium carbonate were added. The mixture was heated to 50 ° C. Stirring was continued until no starting material was detected by HPLC analysis (about 3 hours). The reaction mixture was cooled. The resulting crude solid was stirred in 0 mL of dichloromethane for 30 minutes and then filtered. According to HPLC, the filtered suspended solid was found to be mainly an impurity. The dichloromethane filtrate was dried and evaporated to give 8.75 g of solid. Further drying in the oven resulted in a final weight of 8.67 g. This is a yield of 92.8%.

  (Step 3: 1,3,5,7-tetrakis {3 ′ / 4 ′-[4 ″-(phenylethynyl) phenylethynyl] phenyl} adamantane (TPEPEPA) and 1,3 / 4-bis {1 ′, 3 Synthesis of a mixture of ', 5'-tris (3 "/ 4"-[4' "-(phenylethynyl) phenylethynyl] phenyl} adamantyl} benzene (BTPEPEPAB))

  Following a general protocol for Heck's ethinylation reaction using a palladium catalyst, a mixture of TBPA and BTBPAB (described above) was reacted with 4-ethynyltolan to give 1,3,5,7-tetrakis- {3 ′ / 4. '-[4 "-(phenylethynyl) phenylethynyl] phenyl} adamantane (TPEPEPA) and 1,3 / 4-bis {1', 3 ', 5'-tris {3" / 4 "-[4'"- The final product of a mixture of (phenylethynyl) phenylethynyl] phenyl} adamantyl} benzene (BTPEPEPAB) was obtained.

Example 7
A thermosetting component (a) (200 g) prepared by the same procedure as in Example 5 was placed in a flask. 5.4 times the amount of cyclohexanone of thermosetting component (a) was added to the flask and the flask was shaken. (Wherein, q is 20 to 30) using the adhesion promoter (b) is polycarbosilane _(CH 2 SiH2) q is, the adhesive of 0.268 times the amount of the thermosetting component (a) Accelerator (b) was added to the flask and shaken. The final solution contained 15 wt% thermosetting component (a) and 6.7 wt% polycarbosilane adhesion promoter (b) based on the thermosetting compound (a).

  1 liter three-necked round bottom with a magnetic stir bar, water condenser with N2 inlet and outlet, oil bath with temperature controller and thermocouple, and thermometer with adapter for reflux A flask was used. The solution was heated to reflux for about 23 hours.

  The reaction mixture was cooled to 120 ° C. A Dean-Stark trap was attached and filled with toluene. Toluene in an amount of 0.15 times the thermosetting component (a) in units of ml was added to the refluxing solution. Vigorous boiling and azeotropy began at 130 ° C and continued for about 40 minutes until no more water was generated. The reaction mixture temperature rose to 148 ° C. Toluene and water were extracted from the trap, and azeotropy was continued until toluene and cyclohexanone in an amount 0.165 times that of the thermosetting component (a) were further distilled. The flask temperature reached 153-155 ° C.

  The reaction mixture was cooled to room temperature. Cyclohexanone was added so that the composition of the present invention containing the thermosetting component (a) and the polycarbosilane component adhesion promoter (b) was a 15% by weight solution. The formation of oligomers was confirmed by GPC.

  The following examples relate to the production of layers of the composition of the present invention and layers of the prior art.

Example 8
Comparative Example A is a polyarylene ether taught in US Pat. No. 5,986,045 to Honeywell. In Example 8, the composition of Example 7 was applied to the substrate using the coating conditions in Table II.

  In Table II, BSR means backside cleaning and EBR means end bead cleaning. The coater used was DNS SC-W80A-A VFDLP, the pressurized gas was helium, the supply pressure was 0.08 MPa, the supply rate was 1.0 ml / sec, and the inline filter was 0.1 μm PFFVO1D8S (Millipore (Millipore), Fluoroline-S).

  The spin-coated composition was baked at temperatures of 150 ° C., 200 ° C., and 250 ° C., respectively, for 1 minute under N 2 atmosphere (<50 ppm O 2). Furnace curing conditions were 60 minutes at 400 ° C. in N 2 (15 liters / minute) and increased from 250 ° C. at a rate of 5 ° K / minute. The curing temperature range was 350 ° C to 450 ° C. Alternatively, hot plate curing conditions of 350 ° C. to 450 ° C. for 1 minute to 5 minutes under N 2 atmosphere may be used.

  The resulting layers were analyzed according to the analytical test method described above. The layer properties are shown in Table III.

  A visual test revealed that no streak was present. An increase in Tg is significant for use in harsh high temperature processing environments, and an increase in modulus contributes to product integrity.

Examples 9 to 11
Comparative Example B was a 100% thermosetting compound (a) and did not contain an adhesion promoter (b). In Examples 9 to 11, the compositions of Table IV were prepared according to Example 8 except that the amount of polycarbosilane adhesion promoter (b) was varied. Polycarbosilane component used (B) was _(CH 2 SiH2) q _(wherein, q is 20 to 30).

  Thus, specific embodiments and applications of compositions and methods for producing low dielectric constant polymers have been disclosed. However, it will be apparent to those skilled in the art that many modifications, other than those already disclosed, can be made without departing from the inventive concepts described herein. Accordingly, the spirit of the invention should not be limited except by the appended claims. Moreover, in interpreting both the specification and the claims, all terms should be interpreted in the broadest possible manner consistently within the context. In particular, the terms “including” and “including” should be construed as referring to elements, components, or steps in a non-exclusive sense, and the stated elements, components, or steps Indicates that they can be present, used or combined with elements, components or processes not specifically mentioned.

Considered structure of thermosetting monomer. Considered structure of thermosetting monomer. Considered structure of thermosetting monomer. Considered structure of thermosetting dimer. Considered structure of thermosetting dimer. This is a typical structure of a thermoplastic monomer containing sexiphenylene. This is a typical structure of a thermoplastic monomer containing sexiphenylene. This is a typical structure of a thermoplastic monomer containing sexiphenylene. This is a typical structure of a thermoplastic monomer containing sexiphenylene. 2 is a synthesis scheme of the present invention for a thermosetting monomer. 2 is a synthesis scheme of the present invention for a thermosetting monomer. 2 is a synthesis scheme of the present invention for a thermosetting monomer. This is a synthesis plan for generating a substituted adamantane. Synthetic scheme to produce low molecular weight polymer with pendant cage structure. Synthetic scheme to produce low molecular weight polymer with pendant cage structure. It is a synthetic scheme for producing thermosetting monomers. 2 is the structure of various polymers of the present invention. 2 is the structure of various polymers of the present invention. Synthetic scheme to generate end-capped molecules with pendant cage structure. Synthetic scheme to generate end-capped molecules with pendant cage structure. It is a schematic structure of the low dielectric constant material of this invention. A synthetic scheme for preparing a thermosetting component having at least two isomers. A synthetic scheme for the preparation of Reichert's 1,3,5,7-tetrakis [4 '-(phenylethynyl) phenyl] adamantane (para isomer).

Claims (68)

(A) Structure
Monomer having structure
Or a mixture of the monomer and the dimer wherein Y is selected from a cage compound and a silicon atom, and 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 said aryl, said branched aryl, and said arylene ether has an ethynyl group, R ₇ is aryl or substituted aryl, said R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ have at least two isomers), and
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting component (a), and the composition is applied to a substrate The second functionality is capable of interacting with the substrate.   2. The composition of claim 1, wherein the aryl comprises a moiety selected from the group consisting of (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and (phenylethynyl) phenylphenyl.   The composition of claim 1, wherein Y is selected from the group consisting of adamantane or diamantane.   The composition of claim 1, wherein the monomer is present.   5. The composition of claim 4, wherein the monomer is 1,3,5,7-tetrakis [3 '/ 4'-(phenylethynyl) phenyl] adamantane.   The composition of claim 1, wherein the dimer is present.   7. The composition of claim 6, wherein the dimer is 1,3 / 4-bis {1 ', 3', 5'-tris [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene.   The composition of claim 1, wherein the mixture of the monomer and the dimer is present.   The monomer is 1,3,5,7-tetrakis [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane, and the dimer is 1,3 / 4-bis {1 ′, 3 ′, 5′-tris. 9. The composition of claim 8, which is [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene.   The composition of claim 1, wherein the at least two isomers are meta isomers and para isomers. The adhesion promoter (b)
(I) Formula (I):
Wherein each of R ₈ , R ₁₄ , and R ₁₇ independently represents a substituted or unsubstituted alkylene, cycloalkylene, vinylene, arylene, or arylene, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene, and may be linear or branched, and R ₁₃ is organosilicon, silanyl, siloxyl Or a, b, c, and d satisfy the condition [4 ≦ a + b + c + d ≦ 100,000], and b, c, and d may all be 0, or independently 0 In some cases) polycarbosilane,
(Ii) Formula (R ₁₈ ) _f (R ₁₉ ) _g Si (R ₂₀ ) _h (R ₂₁ ) _i (wherein R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently hydrogen, hydroxyl, Represents unsaturated or saturated alkyl, substituted or unsubstituted alkyl, and the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid group, or aryl, and the above R ₁₈ , R ₁₉ , R ₂₀ , And at least two of R ₂₁ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid group, f + g + h + i ≦ 4)
(Iii) formula _{- [R 22 C 6 H 2} (OH) (R 23)] j - ( _{wherein, R 22} is a substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl or _{aryl,, R 23} Is alkyl, alkylene, vinylene, cycloalkylene, arylene, or aryl, where j = 3-100), phenol-formaldehyde resins or oligomers;
(Iv) glycidyl ether,
(V) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group, and (vi) a vinyl cyclic oligomer or polymer in which the cyclic group is vinyl, aromatic, or heterocyclic aromatic,
The composition of claim 1, wherein the composition is selected from the group consisting of:   The composition according to claim 11, wherein the adhesion promoter (b) is the polycarbosilane.   An oligomer comprising the composition of claim 1.   A spin-on composition comprising the oligomer according to claim 13 and a solvent.   The spin-on composition of claim 14, wherein the solvent is cyclohexanone.   14. A polymer produced from the oligomer of claim 13.   17. A layer comprising the polymer of claim 16.   The layer of claim 17, wherein the dielectric constant of the layer is less than 3.0.   A substrate having on its surface at least one of the layers of claim 17.   A substrate having on its surface at least two of the layers of claim 17.   An electrical device comprising the substrate according to claim 19. (A) Structure
Monomer having structure
Or a mixture of the monomer and the dimer wherein Y is selected from a cage compound and a silicon atom, and 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 said aryl, said branched aryl, and said arylene ether has an ethynyl group, R ₇ is aryl or substituted aryl, said R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ have at least two isomers), and
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting component (a), and the second functionality is with the substrate. A method for improving adhesion to a substrate, comprising applying a layer comprising a composition capable of interacting to the substrate.   23. The method of claim 22, wherein the aryl comprises a moiety selected from the group consisting of (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and (phenylethynyl) phenylphenyl.   23. The method of claim 22, wherein Y is selected from the group consisting of adamantane or diamantane.   23. The method of claim 22, wherein the monomer is present.   26. The method of claim 25, wherein the monomer is 1,3,5,7-tetrakis [3 '/ 4'-(phenylethynyl) phenyl] adamantane.   23. The method of claim 22, wherein the dimer is present.   28. The method of claim 27, wherein the dimer is 1,3 / 4-bis {1 ', 3', 5'-tris [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene.   23. The method of claim 22, wherein the mixture of the monomer and the dimer is present.   The monomer is 1,3,5,7-tetrakis [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane, and the dimer is 1,3 / 4-bis {1 ′, 3 ′, 5′-tris. 30. The method of claim 29, wherein [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene.   23. The method of claim 22, wherein the at least two isomers are meta isomers and para isomers. The adhesion promoter (b)
(I) Formula (I):
Wherein each of R ₈ , R ₁₄ , and R ₁₇ independently represents a substituted or unsubstituted alkylene, cycloalkylene, vinylene, arylene, or arylene, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene, and may be linear or branched, and R ₁₃ is organosilicon, silanyl, siloxyl Or a, b, c, and d satisfy the condition [4 ≦ a + b + c + d ≦ 100,000], and b, c, and d may all be 0, or independently 0 In some cases) polycarbosilane,
(Ii) Formula (R ₁₈ ) _f (R ₁₉ ) _g Si (R ₂₀ ) _h (R ₂₁ ) _i (wherein R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently hydrogen, hydroxyl, Represents unsaturated or saturated alkyl, substituted or unsubstituted alkyl, and the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid group, or aryl, R ₁₈ , R ₁₉ , R ₂₀ , And at least two of R ₂₁ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid group, f + g + h + i ≦ 4)
(Iii) formula _{- [R 22 C 6 H 2} (OH) (R 23)] j - ( _{wherein, R 22} is a substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl or _{aryl,, R 23} Is alkyl, alkylene, vinylene, cycloalkylene, arylene, or aryl, and j = 3-100), phenol-formaldehyde resin or oligomer,
(Iv) glycidyl ether,
(V) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group, and (vi) a vinyl cyclic oligomer or polymer in which the cyclic group is pyridine, aromatic, or heteroaromatic,
23. The method of claim 22, wherein the method is selected from the group consisting of:   33. The method of claim 32, wherein the adhesion promoter (b) is the polycarbosilane. (A) Structure
Wherein Ar is aryl and R ′ ₁ , R ′ ₂ , R ′ ₃ , R ′ ₄ , R ′ ₅ , and R ′ ₆ are independently aryl, branched aryl, arylene ether, and unsubstituted. A thermosetting monomer having a selected aryl, the branched aryl, and the arylene ether each having at least one ethynyl group;
(B) an adhesion promoter comprising at least a bifunctional compound;
The bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting monomer (a), and the composition is applied to a substrate. The second functionality is capable of interacting with the substrate. The adhesion promoter (b)
(I) Formula (I):
Wherein each of R ₈ , R ₁₄ , and R ₁₇ independently represents a substituted or unsubstituted alkylene, cycloalkylene, vinylene, arylene, or arylene, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene, and may be linear or branched, and R ₁₃ is organosilicon, silanyl, siloxyl Or a, b, c, and d satisfy the condition [4 ≦ a + b + c + d ≦ 100,000], and b, c, and d may all be 0, or independently 0 In some cases) polycarbosilane,
(Ii) Formula (R ₁₈ ) _f (R ₁₉ ) _g Si (R ₂₀ ) _h (R ₂₁ ) _i (wherein R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently hydrogen, hydroxyl, Represents unsaturated or saturated alkyl, substituted or unsubstituted alkyl, and the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid group, or aryl, and the above R ₁₈ , R ₁₉ , R ₂₀ , And at least two of R ₂₁ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid group, f + g + h + i ≦ 4)
(Iii) formula _{- [R 22 C 6 H 2} (OH) (R 23)] j - ( _{wherein, R 22} is a substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl or _{aryl,, R 23} Is alkyl, alkylene, vinylene, cycloalkylene, arylene, or aryl, where j = 3-100), phenol-formaldehyde resins or oligomers;
(Iv) glycidyl ether,
(V) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group, and (vi) a vinyl cyclic oligomer or polymer in which the cyclic group is pyridine, aromatic, or heteroaromatic,
35. The composition of claim 34, selected from the group consisting of:   36. The composition of claim 35, wherein the adhesion promoter (b) is the polycarbosilane.   35. A spin-on composition comprising the oligomer of claim 34 and a solvent.   38. The spin-on composition of claim 37, wherein the solvent is cyclohexanone.   38. A layer comprising the spin-on composition of claim 37. (1) (a) Structure
Monomer having structure
Or a mixture of the monomer and the dimer wherein Y is selected from a cage compound and a silicon atom, and 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 said aryl, said branched aryl, and said arylene ether has an ethynyl group, R ₇ is aryl or substituted aryl, said R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ have at least two isomers), and
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality can be the same or different, the first functionality is capable of interacting with the thermosetting component (a), and the composition is applied to a substrate. Providing a composition wherein the second functionality is capable of interacting with the substrate;
(2) generating the low dielectric constant polymer precursor by treating the composition at a temperature of about 30 ° C. to about 350 ° C. for about 0.5 hours to about 60 hours;
A method for producing a low dielectric constant polymer precursor.   41. The method of claim 40, wherein the monomer is present.   42. The method of claim 41, wherein the monomer is 1,3,5,7-tetrakis [3 '/ 4'-(phenylethynyl) phenyl] adamantane.   41. The method of claim 40, wherein the dimer is present.   44. The method of claim 43, wherein the dimer is 1,3 / 4-bis {1 ', 3', 5'-tris [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene.   41. The method of claim 40, wherein the mixture of the monomer and the dimer is present.   The monomer is 1,3,5,7-tetrakis [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane and the dimer is 1,3 / 4-bis {1 ′, 3 ′, 5′-tris 46. The method of claim 45, wherein [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene. The adhesion promoter (b)
(I) Formula (I):
Wherein each of R ₈ , R ₁₄ , and R ₁₇ independently represents a substituted or unsubstituted alkylene, cycloalkylene, vinylene, arylene, or arylene, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene, and may be linear or branched, and R ₁₃ is organosilicon, silanyl, siloxyl Or a, b, c, and d satisfy the condition [4 ≦ a + b + c + d ≦ 100,000], and b, c, and d may all be 0, or independently 0 In some cases) polycarbosilane,
(Ii) Formula (R ₁₈ ) _f (R ₁₉ ) _g Si (R ₂₀ ) _h (R ₂₁ ) _i (wherein R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently hydrogen, hydroxyl, Represents unsaturated or saturated alkyl, substituted or unsubstituted alkyl, and the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid group, or aryl, R ₁₈ , R ₁₉ , R ₂₀ , And at least two of R ₂₁ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid group, f + g + h + i ≦ 4)
(Iii) formula _{- [R 22 C 6 H 2} (OH) (R 23)] j - ( _{wherein, R 22} is a substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or _{arylene,, R 23} Is alkyl, alkylene, vinylene, cycloalkylene, arylene, or aryl, and j = 3-100), phenol-formaldehyde resin or oligomer,
(Iv) glycidyl ether,
(V) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group, and (vi) a vinyl cyclic oligomer or polymer in which the cyclic group is pyridine, aromatic, or heteroaromatic,
41. The method of claim 40, wherein the method is selected from the group consisting of: (1) (a) Structure
Monomer having structure
Or a mixture of the monomer and the dimer wherein Y is selected from a cage compound and a silicon atom, and 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 said aryl, said branched aryl, and said arylene ether has an ethynyl group, R ₇ is aryl or substituted aryl, said R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ have at least two isomers), and
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the thermosetting component (a), and the composition is applied to a substrate And wherein the second functionality provides an oligomer capable of interacting with the substrate;
(2) A method for producing a low dielectric constant polymer, comprising polymerizing the oligomer to produce the low dielectric constant polymer, wherein the polymerization comprises a chemical reaction of the ethynyl group.   49. The method of claim 48, wherein Y is selected from the group consisting of adamantane and diamantane.   49. The method of claim 48, wherein the aryl comprises a moiety selected from the group consisting of (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and (phenylethynyl) phenylphenyl.   49. The method of claim 48, wherein at least three of the aryl, the branched aryl, and the arylene ether have an ethynyl group and the polymerization comprises a chemical reaction of at least two of the ethynyl groups.   49. The method of claim 48, wherein the aryl, the branched aryl, and the arylene ether all have an ethynyl group and the polymerization comprises a chemical reaction of an ethynyl group.   49. The method of claim 48, wherein the monomer is present.   54. The method of claim 53, wherein the monomer is 1,3,5,7-tetrakis [3 '/ 4'-(phenylethynyl) phenyl] adamantane.   49. The method of claim 48, wherein the dimer is present.   56. The method of claim 55, wherein the dimer is 1,3 / 4-bis {1 ', 3', 5'-tris [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene.   49. The method of claim 48, wherein the mixture of the monomer and the dimer is present.   The monomer is 1,3,5,7-tetrakis [3 ′ / 4 ′-(phenylethynyl) phenyl] adamantane, and the dimer is 1,3 / 4-bis {1 ′, 3 ′, 5′-tris. 58. The method of claim 57, which is [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene.   49. The method of claim 48, wherein the at least two isomers are meta isomers and para isomers.   49. The method of claim 48, wherein the thermosetting component (a) is dissolved in a solvent. The adhesion promoter (b)
(I) Formula (I):
Wherein each of R ₈ , R ₁₄ , and R ₁₇ independently represents a substituted or unsubstituted alkylene, cycloalkylene, vinylene, arylene, or arylene, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene, and may be linear or branched, and R ₁₃ is organosilicon, silanyl, siloxyl Or a, b, c, and d satisfy the condition [4 ≦ a + b + c + d ≦ 100,000], and b, c, and d may all be 0, or independently 0 In some cases) polycarbosilane,
(Ii) Formula (R ₁₈ ) _f (R ₁₉ ) _g Si (R ₂₀ ) _h (R ₂₁ ) _i (wherein R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently hydrogen, hydroxyl, Represents unsaturated or saturated alkyl, substituted or unsubstituted alkyl, and the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid group, or aryl, and the above R ₁₈ , R ₁₉ , R ₂₀ , And at least two of R ₂₁ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid group, f + g + h + i ≦ 4)
(Iii) formula _{- [R 22 C 6 H 2} (OH) (R 23)] j - ( _{wherein, R 22} is a substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl or _{aryl,, R 23} Is alkyl, alkylene, vinylene, cycloalkylene, arylene, or aryl, where j = 3-100), phenol-formaldehyde resins or oligomers;
(Iv) glycidyl ether,
(V) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group, and (vi) a vinyl cyclic oligomer or polymer in which the cyclic group is pyridine, aromatic, or heteroaromatic,
49. The method of claim 48, wherein the method is selected from the group consisting of: (A) a first main chain having a first aromatic moiety and a first reactive group, a second main chain having a second aromatic moiety and a second reactive group (the first and second Two main chains are cross-linked by the first and second reactive groups in a cross-linking reaction), and a cage structure that is covalently bonded to at least one of the first and second main chains (the cage structure is at least An adhesion promoter comprising a compound having 8 atoms), and (b) a compound that is at least difunctional;
Wherein the bifunctionality may be the same or different, the first functionality is capable of interacting with the first and second backbones, and the material is a substrate When applied to a spin-on low dielectric constant material, wherein the second functionality is capable of interacting with the substrate.   64. The spin-on low dielectric constant material of claim 62, wherein the aromatic moiety comprises phenyl.   64. The spin-on low dielectric constant material of claim 62, wherein at least one of the first reactive group or the second reactive group comprises an ethynyl group.   64. The spin-on low dielectric constant material of claim 62, wherein the cage structure comprises at least one of adamantane and diamantane.   64. The spin-on low dielectric constant material of claim 62, wherein the cage structure has a substituent. The adhesion promoter (b)
(I) Formula (I):
Wherein each of R ₈ , R ₁₄ , and R ₁₇ independently represents a substituted or unsubstituted alkylene, cycloalkylene, vinylene, arylene, or arylene, and R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene, and may be linear or branched, and R ₁₃ is organosilicon, silanyl, siloxyl Or a, b, c, and d satisfy the condition [4 ≦ a + b + c + d ≦ 100,000], and b, c, and d may all be 0, or independently 0 In some cases) polycarbosilane,
(Ii) Formula (R ₁₈ ) _f (R ₁₉ ) _g Si (R ₂₀ ) _h (R ₂₁ ) _i (wherein R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ are each independently hydrogen, hydroxyl, Represents unsaturated or saturated alkyl, substituted or unsubstituted alkyl, and the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid group, or aryl, and the above R ₁₈ , R ₁₉ , R ₂₀ , And at least two of R ₂₁ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid group, f + g + h + i ≦ 4)
(Iii) formula _{- [R 22 C 6 H 2} (OH) (R 23)] j - ( _{wherein, R 22} is a substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl or _{aryl,, R 23} Is alkyl, alkylene, vinylene, cycloalkylene, arylene, or aryl, where j = 3-100), phenol-formaldehyde resins or oligomers;
(Iv) glycidyl ether,
(V) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group, and (vi) a vinyl cyclic oligomer or polymer in which the cyclic group is pyridine, aromatic, or heteroaromatic,
64. The spin-on low dielectric constant material of claim 62, selected from the group consisting of: (A) a polymer having pendant cage structure _{- [OR 24 (R 25)} m OR 26] n - ( _{wherein, R 24} is _-C 6 _{H 3, R 25} is adamantane, diamantane, _(C 6 H _{5) p} is (adamantane), or _{(C 6} H _{5) p} (diamantane), an m = 1 to 3, a n = 1 to 10 ^3, a p = 0 or _{1, R 26} is 2,3,4,5- (tetraphenyl) cyclodienone-1 or
)
(B) an adhesion promoter comprising at least a bifunctional compound;
Wherein the bifunctionality can be the same or different, the first functionality can interact with the polymer, and when the polymer is applied to a substrate, A spin-on low dielectric constant polymer, wherein the second functionality is capable of interacting with the substrate.