TW200408662A - Organic compositions - Google Patents

Abstract

The present composition provides a composition comprising: (a) thermosetting component wherein the thermosetting component comprises monomer having the structure, dimer having the structure, or a mixture of the monomer and the dimer wherein Y is selected from cage compound and silicon atom; R1, R2, R3, R4, R5, and R6 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; R7 is aryl or substituted aryl; and at least one of the R1, R2, R3, R4, R5, and R6 comprises at least two isomers; and (b) adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the thermosetting component (a) and the second functionality is capable of interacting with a substrate when the composition is applied to a substrate. The present composition is particularly useful as a dielectric material in microelectronic applications.

Description

200408662 先前 Brief description of the previous technology, content, implementation and drawings) (弋 明 ϊϋϊ9月了 Ϊ 明 的 所属 的 技术 领域 范发明 转 发明 的 This invention relates to semiconductor devices, and in particular, to having organic low Semiconductor devices with dielectric constant materials and methods of manufacturing the same. BACKGROUND OF THE INVENTION In order to increase the performance and speed of semiconductor devices, semiconductor device manufacturers seek to reduce the spacing and space of interconnects, while minimizing transmission losses and reducing the cost of interconnects. Capacitive coupling. One way to eliminate power loss and reduce capacitance is to reduce the dielectric constant (also known as "k") of the insulating material or dielectric of the discrete interconnect. Insulating materials with low dielectric constant are particularly suitable, Because it generally allows faster signal propagation, reduces crosstalk between capacitors and conductor lines, and reduces the voltage required to drive integrated circuits. Because air has a dielectric constant of 1.0, the main goal is to reduce the dielectric constant of the insulator material to The theoretical limit is 1.0, and several methods of reducing the dielectric constant of insulating materials have been used in this art. These techniques include the addition of elements such as fluorine to the composition to reduce the dielectric constant of bulk materials. Other methods of reducing k include the use of alternative dielectric material matrices. Therefore, as interconnect spacing decreases, the need for insulator materials The concomitant reduction of the dielectric constant to achieve improved performance and speed of future semiconductor devices. For example, devices with interconnect pitches of 0.13 or 0.10 microns and below seek insulation materials with a dielectric constant (k) < 3. Currently used Variations of silicon dioxide (SiO2) and 5.02 such as fluorinated silicon dioxide or fluorinated silica glass (hereinafter referred to as FSG). These dioxides with a dielectric constant of about 3.5-4.0 are common Used as a dielectric for semiconductor devices. Although 200408662 (2) 51〇2 and FSG have the mechanical and thermal stability required to resist the thermal cycling and processing steps of semiconductor device manufacturing, the industry desires a lower dielectric constant The methods used to deposit dielectric materials can be divided into two categories: spin-on deposition (hereinafter referred to as > SOD) and chemical vapor deposition (hereinafter referred to as CVD). Several methods of developing lower dielectric constants This includes changing the chemical composition (organic, inorganic or blend of organic and inorganic) or changing the dielectric matrix (porous, non-porous). Table 1 outlines several materials with a dielectric constant of 2.0 to 3.5. (PE = reinforced HDP = High Density Plasma). However, the dielectric materials® and substrates disclosed in the bulletin shown in Table 1 cannot show the proper or even required combination of physical and chemical properties of effective dielectric materials, such as higher Mechanical stability, high thermal stability, high glass transition temperature, high modulus or hardness, while still being fused, spun or deposited on substrates, wafers or other surfaces. Therefore, other uses for dielectrics can be investigated Compounds and materials of materials and layers, even if such compounds or materials are not currently considered to be dielectric materials in their present form.

200408662 (3)

Table 1 Dielectric constant of material deposition method (k) Reference document Fluorination and Oxidation (SiOF) PE-CVD; HDP-CVD 3.3-3.5 US Patent 6,278,174 Hydrogen Silsesquioxane (HSQ) SOD 2.0-2.5 United States Patents 4,756,977; 5,370,903; and 5,486,564; International Patent Publication WO00 / 40637; ES Moyer et al., &Quot; Ultra-low-k Shixii semi-oxygen fired base resin ", Concepts and Needs for Low Dielectric Constant < 0.15 μιη Interconnect Materials: Now and the Next Millennium, Sponsored by the American Chemical Society, pages 128-146 (November 14-17, 1999) Methylsilsesquioxane (MSQ) SOD 2.4-2.7 U.S. Patent 6,143,855 Polyorganic Fragments SOD 2.5-2.6 U.S. patent 6,225,23 8 Fluorinated amorphous carbon (aC: F) HDP-CVD 2.3. U.S. patent 5,900,290 Benzocyclobutene (BCB) SOD 2,4-2.7 U.S. patent 5,225,586 Polyarylene ether ( PAE) SOD 2.4 U.S. Patent Nos. 5,986,045; 5,874,516; and 5,658,994 Parylene (N and F) CVD 2.4 U.S. Patent No. 5,268,202 SOD 2.6 U.S. Patent No. 5,965,679 &6,288,188B1; Integration of semiconductor dielectrics Feasibility 'Proc. Ofthe 2001 International Interconnect Tech. Conf., Pp. 253-254 (2001). However, in many developing S〇D an organic dielectric constant of 2.0 and 3.5

The system has certain disadvantages based on the above-mentioned mechanical and thermal characteristics; therefore, there is an industrial need to develop improved processing and performance of dielectric films in this range of dielectric constants. -10- 200408662 (4)

Reichert and Mathias illustrate compounds and ceremonies, which include diamond molecules, which are types of cage-based molecules and are taught to be useful as diamond substrates. (Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1993, Vol. 34 (1), pp. 495-6; Polym, Prepr. (Am · Chem · Soc ·, Div · Polym. Chem.), 1992, Vol. 33 (2), pp. 144-5; Chem. Mater., 1993, Vol. 5 (1), pp. 4-5; Macromolecules, 1994, Vol. 27 (24 ), pp. 7030-7034;

Macromolecules, 1994, Vol. 27 (24), pp. 7015-7023; Polym, Prepr. (Am. Chem. Soc ·, Div. Polym · Chem ·), 1995, Vol. 36 (1), pp. 741- 742; 205th ACS National Meeting, Conference Program, 1993, pp. 312; Macromolecules, 1994, Vol. 27 (24), pp. 7024-9;

Macromolecules, 1992, Vol. 25 (9), pp. 2294-306; Macromolecules, 1991, Vol. 24 (18), pp. 5232-3; Veronica R. Reichert, PhD

Dissertation, 1994, Vol. 55-06B; ACS Symp. Ser .: Steps in high-performance materials-growing polymers, 1996, Vol. 624, ρ.197-207; Macromolecules, 2000, Vol. 33 (10), pp 3 855-3859; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1999, Vol. 40 (2), pp. 620-62 1; Polym, Prepr. (Am. Chem. Soc ·, Div. Polym. Chem ·), 1999, Vol. 40 (2), pp. 577-78; Macromolecules, 1997, Vol. 30 (19), pp. 5970-5975; J. Polym. Sci. Part A: Polymer Chemistry, 1997, Vol. 35 (9), pp. 1743-1751; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1996, Vol. 37 (2), pp. 243-244; Polym, Prepr · (Am · Chem · Soc ·, Div. Polym. Chem ·), 1996, Vol. 37 (1), pp. 551-552; J. Polym. Sci., Part A : Polymer Chemistry, 1996, Vol. 34 (3), pp. 397-402; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1995, Vol. 36 (2), pp. 140-141; Polym, Prepr. (Am. -11-200408662 (5)

Chem. Soc., Div. Polym. Chem.), 1992, Vol. 33 (2), p. 146-147; J.

Appl. Polym. Sci., 1998, Vol. 68 (3), p. 475482). Reichert and

The adamantyl base compounds and monomers described by Mathias are best used to form polymers with aramid molecules at the core of thermoset materials. However, the compounds shown by the Reichert and Mathias study were designed to include isomers of only one adamantyl base compound. Structure A shows this symmetry. Para-isomer 1,3,5,7-[[4 '-(phenylethynyl) phenyl] adamantane:

Structure A

In other words, Reichert and iMathias, in their respective work together, consider useful polymers to contain only one isomer form of the target adamantyl base monomer. However, when starting from a single isomer (symmetrical, all para ,, isomer), the adamantyl base monomer is 1,3,5,7-[[·· ((phenylethynyl) phenyl]] Apparently there is a problem in the formation and processing of the adamantane polymer. According to Reichert's discussion (above) and! \ 1 & (: 1: 〇111〇 ^ (: 111 € 5, 〇1.27, (卩 9.701 5-7034) ) 'Are found that the symmetrical all para-isomer 1,3,5,7-^ [4 ^ (phenylethynyl) phenyl] adamantane 200408662 ⑹ can be sufficiently dissolved in chloroform, and 1H NMR spectrum can be obtained However, it was found that the search time to resolve the 13C NMR spectrum was not practical, indicating that the all-isomeric ft has a low solubility. Therefore, Reichert's symmetry is "all-para-" 'isomer 1,3,5,7 -The [W- (phenylethynyl) phenyl] adamantane is not soluble in standard solvents, so it cannot be used in any application that requires solubility or solvent-based processing such as flow coating, spin coating or dipping Coating. Refer to Comparative Example 1 below. In the patent application PCT / US 01/22204, jointly filed by the applicant, etc., an application was found on October 17, 2001. Compositions containing a mixture of isomeric thermosetting monomers or dimers, wherein the mixture contains at least one monomer or dimer having the following structure

Ri R4

R2

Y is selected from cage compounds and silicon atoms; Ri, R2, R3, R4, R5, and R6 are independently selected from aryl, branched aryl, and aryl mystery; aryl, branched aryl, and aryl ether At least one of them has an ethynyl group; R7 is an aryl group or a substituted aryl group. Applicants and others also disclose methods for forming such thermosetting mixtures. This mixture of neomeric thermosetting monomers or dimers can be used as a dielectric material for microelectronic applications, lr dielectric materials and can be dissolved in many solvents such as cyclohexane. These desirable characteristics > can make this heterogeneous thermosetting monomer or dimer mixture suitable for film formation with a thickness of about 0.1 micrometer to about 1.0 micrometer. • 13-200408662

⑺ Although various methods are known in the art of reducing the dielectric constant of materials, these methods also have disadvantages. Therefore, there is still a need in the semiconductor industry, a) to provide improved compositions and methods for reducing the dielectric constant of the dielectric layer: method; b) to provide improved mechanical properties such as thermal stability, glass transition temperature (Tg), and hardness Dielectric materials; and c) manufacturing thermosetting compounds and dielectric materials that are soluble and spin-formed into wafers or layered materials. SUMMARY OF THE INVENTION In response to the needs of this technology, applicants and others have developed a composition comprising: (a) a thermosetting component, wherein the thermosetting component comprises a monomer having the following structure

Ri

R2 R3 Dimer with the following structure

Ri R4

R5

Rs R6 or a mixture of monomers and dimers, wherein γ is selected from cage compounds and silicon atoms; Ri, R2, R3, R4, R5 and R6 are independently selected from aryl, branched aryl, and Shenfang and ; At least one of the aryl group, pendant aryl group, and fangfang mystery has ethyl block: -14-200408662 fluorenyl group; 117 is aryl group or substituted aryl group; and R! At least one containing at least two isomers; and (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, and the first functionality may interact with the thermosetting component (a) When the composition is applied to a substrate, the second functionality can interact with the substrate. Preferably, the adhesion promoter is selected from the group consisting of: (i) polycarbosilane of formula (I): ΗISi- R9

Rs-

Rio-Si—

Rn r12 • Si—R24- 〇 ~ ^ 13 a b

Rl5Si —R17—I Rl6 wherein R8, R14, and R 17 each independently represent a substituted or unsubstituted alkylene, cycloalkylene, vinylidene, allyl, or arylene; R9, Rio, Rh, R12, R15, and R16 each independently represent a hydrogen atom, an alkyl group, an alkylene group, a vinyl group, a cycloalkyl group, an allyl group, an aryl group, or an arylene group and may be a straight chain or a branched chain; R π represents an organic fragment, Crushed alkoxy group, crushed oxy group or organic group; and a, b, c and d meet the conditions of [4Sa + b + c + dS100,000], and b and c and d may be zero together or independently; (ii) Formula (RtOKRehSKRuhiRnh silane, where R18, R19, R20 and R21 each independently represent hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkylene, wherein the substituent is amine or epoxy, not A saturated or saturated alkoxy group, an unsaturated or saturated polyacid group, or an aryl-15-200408662 (9) group; and at least two of R18, R19, R20, and R21 represent hydrogen, a hydroxyl group, a saturated or unsaturated alkoxy group , Unsaturated alkyl or unsaturated carboxylic acid groups; and f + g + h + i <4; (iii) a phenol-formaldehyde tree moth or oligomer of the formula-[Ι122 [: 6Η2 (〇Η) (I123)] ''- Where R22 is substituted or unsubstituted alkylene, cycloalkylene, ethenyl, allyl or aryl; R23 is alkyl, alkylene, vinylene, cycloalkylene, allylene Or aryl; and j = 3-100; (iv) a glycidyl chain;

(v) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group; and (i) a vinyl cyclic oligomer or polymer, wherein the cyclic group is pyridine, an aromatic hydrocarbon, or a heteroaromatic hydrocarbon. The applicant and the like have also developed a method for improving adhesion to a substrate, comprising the steps of: applying a composition layer to the substrate, the composition layer comprising: (a) a thermosetting component, wherein the thermosetting component includes a monomer

Ri r4

R2 —R3 Dimer with the following structure • 16- 200408662 (ίο)

Rl R4

Ri. ,, f R3 JYllUlUntn "·. R5 R6 or a mixture of monomers and dimers, wherein Y is selected from cage compounds and silicon atoms; R1, R2, R3, R4, 115 and R6 are independently selected from aromatic At least one of aryl, branched-chain aryl, and arylene ether has ethynyl; 117 is aryl or substituted aryl; and Ri, R2, R3, R4, R5, and At least one of R6 contains at least two isomers; and (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, and the first functionality may be the same as the thermosetting component (a) The second functionality can interact with the substrate. In addition, the applicant and the like have also developed a composition comprising: (a) a thermosetting monomer having the following structure

Ar, R, 44 R, 3 where Aγ is aryl; Rf 丨, R'2, IΓ3, R, R, and 11'6 are independently selected from aryl, branched aryl, and arylene ether, and are unsubstituted ; And aryl, branched-chain aryl, and arylene ether each having at least one ethynyl group; and (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, first. The functionality can interact with the thermosetting component (a) and when Composition-17 · 200408662 ⑼ is applied to a substrate, the second functionality can interact with the substrate. The adhesion promoter (b) is preferably selected from (i) polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (iv) glycidol chain, (v) unsaturated polyacid Or (vi) the acetamidinyl cyclic oligomer or polymer. In addition, applicants and others have also developed a method for manufacturing a low-dielectric-constant polymer precursor or oligomer, comprising the steps of: (1) providing a composition comprising: (a) a thermosetting component, wherein the thermosetting component Contains monomers having the following structures

Ri r4

R2 R3 Dimer with the following structure

Rl R4

R2 ·

R3 丨 丨 chuan 丨 丨 R5 or a mixture of monomers and dimers, where γ is selected from cage compounds and silicon atoms; R1, R2, R3, R4, R5 and R6 are independently selected from aryl, branched aromatic And aryl ether; at least one of aryl, branched aryl and aryl ether has ethynyl; R7 is aryl or substituted aryl; and at least one of Ri, R2, R3, chi 4, R5, and R6 Contains at least two isomers; and (b) an adhesion promoter, package-18-200408662

(12) Contains a compound having at least difunctionality, wherein the difunctionality may be the same or different, the first functionality may interact with the thermosetting component (a) and when the composition is applied to a substrate, the second functionality It can interact with the substrate; and: (2) treating the composition at a temperature of about 30 ° C to about 350 ° C for about 0.5 to about 60 hours to form the low dielectric constant polymer precursor. The adhesion promoter (b) is preferably selected from (i) polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (iv) glycidyl ether, (v) unsaturated carboxylic acid ester or (Vi) The above-mentioned vinyl cyclic oligomer or polymer. In addition, applicants and others have also developed a method for manufacturing a low dielectric constant polymer, which includes the following steps: (1) providing an oligomer comprising (a) a thermosetting component, wherein the thermosetting component includes Monomers of the following structures

Ri

Dimer with the following structure

Ri r4 or a mixture of monomers and dimers, where Y is selected from cage compounds and silicon-19-200408662 (13) atoms; Ri, R2, R3, R4, R5 and R6 are independently selected from aryl and branched chains Aryl and arylene ether; at least one of aryl, branched aryl and arylene has ethynyl; 117 is aryl or substituted aryl; and Ri, R2, R3, R4, R5 and R6: at least One containing at least two isomers; and (b) an adhesion promoter, including-containing a compound having at least difunctionality, wherein the difunctionality may be the same or different, and the first functionality may be the same as the thermosetting component (a) Interaction when the composition is applied to a substrate, the second functionality may interact with the substrate; and (2) polymerize the oligomer to form a low dielectric constant polymer, where the polymerization includes the acetylene group chemistry reaction. The adhesion promoter (b) is preferably selected from (i) ® polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (iv) glycidic acid, (v) unsaturated acid acid vinegar Or (vi) the acetamidinyl cyclic oligomer or polymer. In addition, the applicant and the like have also developed a low-spin dielectric constant material comprising: (a) a first main chain having a first aromatic hydrocarbon moiety and a first reactive group and a second aromatic hydrocarbon moiety and a second reactive reagent The second main chain of the group, wherein the first and second main chains are crosslinked by the first and second reactive groups in the crosslinking reaction, and the cage structure is covalently bonded to the first and At least one in the second main chain, wherein the cage structure contains at least 8 atoms; (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionalities may be the same or different, the first functionality It can interact with the first and second main chains and when the material is applied to the substrate, the difunctionality can interact with the substrate. β-adhesion promoter (b) is preferably selected from (i) polycarbosilane, (Π) silane, (iii) phenol-w formaldehyde resin or oligomer, (iv) glycidyl ether, (v) unsaturated A carboxylic acid ester or (vi) the vinyl cyclic oligomer or polymer described above. -20- 200408662 (14) The various objects, characteristics, aspects and advantages of the present invention will be made clearer by the following detailed description of the preferred specific examples of the present invention together with the accompanying drawings. Brief Description of the Drawings Table 1 shows several representative teachings on low dielectric materials. 1A-1C are expected structures of thermosetting monomers. Figure ID-1E is the expected structure of a thermosetting dimer. 2A-2D are typical structures of a thermosetting monomer containing hexaphenylene. 3A-3C are schematic diagrams of the expected synthesis of a thermosetting monomer. FIG. 4 is a synthetic scheme for generating substituted diamond firing. Figure 5 is a synthetic scheme for producing a low molecular weight polymer having a hanging cage structure. Figure 6 is a synthetic scheme for producing a low molecular weight polymer having a hanging cage structure. FIG. 7 shows a synthetic scheme for generating a thermosetting monomer. Figures 8A-B are structures of various desired polymers. Figures 9A-B are synthetic schemes 3 for generating end capping molecules with a hanging cage structure. Figure 10 is a schematic structure of an expected low dielectric constant material. Fig. 11 is a synthetic scheme for preparing a thermosetting component containing at least two isomers. Fig. 12 is a synthetic scheme of 1,3,5,7-[[4 '-(phenylethynyl) phenyl] adamantane (para-isomer) of Reichert prepared. Detailed description of the invention The term "at least two monomers" as used herein means at least two selected from among 21-200408662

(15) Different isomers of isomers, para and ortho positions. These at least two isomers are preferably meta and para isomers. As used herein, the term "low dielectric constant polymer" means an organic, organometallic, or inorganic polymer having a dielectric constant: number of about 3.0 or less. Low dielectric materials are generally manufactured in the form of thin films having a thickness of 100 to 25,000 Angstroms, but they can also be used as thick films, lumps, cylinders, balls, and the like. As used herein, the term "backbone" means a continuous chain of atoms or portions forming a polymeric strand, which is covalently bonded such that the removal of any atom or moiety can cause chain disruption. · Terms used herein 〃Reactive group " means that any atom, functionality, or group is sufficiently reactive to form at least one covalent bond with another reactive group in a chemical reaction. The chemical reaction can be at the same or two separations Occurs between two identical or different reactive groups on the main chain. It is also expected that the reactive groups may react with one or more second or outer crosslinked molecules to crosslink the first and second main chains. Although cross-linking without external cross-linking agents presents various advantages, including reducing the total number of reactive groups in the polymer and reducing the number of reaction steps required, cross-linking without external cross-linking agents also has some disadvantages. For example, it is generally not possible to adjust the amount of cross-linking functionality. On the other hand, when the polymerization reaction and the cross-linking reaction are chemically incompatible, an external cross-linking agent may be used. The term "cage structure" used in the present invention "Cage-like molecules" and "cage-like, ψ compounds" are intended to be used interchangeably and mean that molecules or molecules arranged with at least 8 atoms, such that at least one bridge is covalently connected to two or more atoms of the ring system In other words, a cage structure, a cage molecule, or a cage compound contains more than 22-200408662 (16) covalently bonded rings; ^ $, μ ^ ring, where the structure, molecule or compound is bounded "A plate" makes it impossible for a point located inside the plate to leave the plate without passing through the ring. The bridge and / or ring system may contain one or more heteroatoms and may include: 10,000 L groups, localized or non-rings Residues and hydrocarbon groups are either partially cyclized or non-, unsaturated hydrocarbon groups. It is further expected that cage structures include fullerenes (fUllereneS) and crown ethers with at least one bridge. For example, adamantane is Are considered cage-like structures, and naphthalene or aromatic hydrocarbon spiro compounds are not considered dragon-like compounds within the scope of this definition 'because tea or aromatic tobacco spiro compounds do not have one or more bridges, Said Lu Mingne. As used herein, the term “adhesive accelerator” means that any component, when added to the thermosetting component ㈤ or the polymer, can improve its adhesion to the substrate than the thermosetting component ㈤ or the polymer alone. This article The term used, a compound with major and minor ambiguities " means any component having two functional groups that can interact or react with each other or form the following bonds. Functional groups can react in various ways, including addition reactions , Nucleophilic or electrophilic substitution or elimination, radiation reaction. In addition, alternative reactions can also include non-covalent bonds _ such as the formation of Van der Waals, electrostatic bonds, ionic bonds and hydrogen bonds. Used in this paper The term "layer" includes films and coatings. Thermoset (a): The thermoset (a) and the polymer are disclosed in the commonly assigned application sn 09/618945 'July 19, 2000; USSN 〇 9/897936, filed July 5, 2001; PCT / US01 / 22204, filed October 17, 2001; US SN * 1 09/54505 8, filed April 7, 2000; and US SN 09 / 902924, 2001 7 -23-200408662

The application is filed for the month, which is incorporated herein by reference. The thermosetting component (a) contains a monomer having a general structure shown in Structure 1A

Ri R4

R3 (Structure 1A) Dimer with a general structure shown in Structure 1B

· &Quot; ... · Rs (structure 1B), or a mixture of monomers and dimers, where Y is selected from cage compounds and silicon atoms; Ri, R2, R3, R4, 115 and R6 are independently selected Aryl, branched aryl, and arylene ether; at least one of aryl, branched aryl, and arylene ether has ethyl block; R7 is aryl or substituted aryl ^ where the substituents are alkyl and halide Or aryl. The term "aryl" as used herein means without further description any type of aryl group, which may include, for example, branched aryl groups or arylene ethers. Y is preferably adamantane or adamantane. Typical structures of thermosetting monomers Objects including adamantane, adamantane and silicon atoms are shown in Figures IA, 1B and 1C, respectively, where η is an integer between 0 and 5 or more. Typical structures of thermosetting dimers include adamantane and gold-24-200408662 ( 18) Freshly fired are shown in Figure 1] 3 and 1E, respectively, where η is an integer between 0 and 5 or more. In the thermosetting component (a), it is preferred to present a mixture of monomers and dimers. The mixture preferably contains About 95-97% by weight of the monomer and about 3% by weight of the dimer. Or, the thermosetting component (a) has the general structure shown in Structure 2:

Rfi R, 6, AI / R2

Ar.

P, / I R5 R, R3 (Structure 2) where Ar is an aryl group, and RVR, 6 is independently selected from aryl, branched aryl, aryanoic acid without substitution, and aryl and branched aryl And aryl ether each have one ethyl group. Typical structures of thermosetting monomers include four and six substituted hexabenzines, respectively, as shown in Fig. 2A and 2C_2E). The thermosetting monomers generally shown in structures 丨 VIII and ⑺ and 2 can be provided by various synthetic pathways'. Typical synthesis techniques for structures 1A, 1B, and 2 are shown in Figures 3A-3C. Figure 3A description and Example 5 illustrate a preferred synthetic route for the production of the expected thermosetting monomers with adamantane as a cage compound, in which bromoarene is acetylated with phenyl in a palladium-catalyzed Heck reaction. First, according to the aforementioned procedure (J. Org. Chem. 45, 5405-5408 (1980), Sollot, GPC and Gilbert, E · E ·) bromodamantane (1) is brominated to 1,3,5,7-tetra Bromoadamantane (TBA) (2J. TBA reacts with brominated benzene to give 1,3,5,7-tetra (3, / 4 · -bromophenyl) adamantane (TBPA) 〇_), as described in Macromolecules , 27, 7015-7022 (1990), Reichert, VR and Mathias LJ. TBPA followed the reaction with a substituted acetylene aryl group in a palladium-catalyzed Heck reaction according to standard reaction procedures to obtain 1, 3, 5, 7 · [ 3 / 4- (arylethenyl) phenyl] adamantine (raw). Example 5 continues to show the differences between Reichert's work and Invention-25 · 200408662 (19) background compounds and the expected thermosetting component (a), "Heck reaction catalyzed by palladium can also be used for thermosetting monomers and hexaphenylene as aromatic hydrocarbons. Partial synthesis is shown in Figures 2A-2D, in which tetrabromohexadecene and hexabromo-hexadecene are reacted with an acetylene aryl compound to obtain the desired enantiomeric thermosetting monomer. Alternatively, TBA can be converted to a hydroxyarylated adamantane, which is subsequently converted to a thermosetting monomer in a nucleophilic arene substitution reaction. In FIG. 3B, TBAU) is produced from diamond firing (JJ as described above, and further reacts with phenol in the electrophilic tetrasubstitution to obtain 1,3,5,7-((374, hydroxyphenyl) adamantane ( THPA) (i). Alternatively, TBA can also be reacted with anisole to obtain 1,3,5,7 · (3V4'-methoxyphenyl) adamantane (magic, which can be further reacted with Βγ3 to obtain (THPA) (i). THPA can then use standard procedures (for example, Engineering Plastics-Polyarene Chain Manual, RJ Cotter, Gordon and Breach Publishers, ISBN 2-88449- 112-0) in various pro Nuclear aromatics are reacted with activated fluoroaromatics to produce the desired thermosetting monomer, or THPA can be reacted with 4-halo-4'-fluorodiphenylacetylene (halogen Group = Br or I) to obtain 1,3,5,7-{{3 '/ 4'-[4 "-(halophenylethynyl) phenoxy] phenyl} adamantane α). In another alternative reaction, various alternative reactants can also be used to generate thermosetting monomers. Similarly, the nucleophilic aromatic substitution reaction can also be used for thermosetting monomers and hexaphenylene as aromatic compounds. In part of the synthesis, hexaphenylene is reacted with 4-fluorodiphenylethyl block to produce thermosetting monomers. Alternatively, m-cyclohexanetriol can be reacted with 4- [4 '· (fluorobenzene) in a standard aromatic substitution reaction. Acetylethynyl) phenylethynyl] benzene to give .1,3,5-gins {4 '-[4 "-(phenylethynyl) phenylethynyl] phenoxy} 200408662 (20) benzene. When the cage compound is a silicon atom, a typical preferred synthetic scheme is shown in FIG. 3C, in which bromine (phenylethynyl) arene arms (and) (where η is an integer between 0 and 5 or more) ) Into the corresponding (phenylethynyl) aryl lithium arm, (23, which is subsequently reacted with silicon tetrachloride to obtain the desired star-shaped thermosetting monomer having a silicon atom as a cage compound (1 0) The cage compound is preferably a silicon atom, adamantane, adamantane, or some adamantane or adamantane. In another aspect of the subject matter of the present invention, various cage compounds other than adamantane or adamantane are also contemplated. Note that the molecular size of the cage compound and the total length of the combined arms Ri-116 or the configuration will determine the final low dielectric constant polymer Dry physical properties and mechanical properties (by steric hindrance effect). Therefore, when quite small cage compounds are desirable, substituted and derivatized adamantane, adamantane, and relatively small bridged cyclic aliphatic and aromatic compounds (usually having Less than 15 atoms). In contrast, when larger cage compounds are appropriate, larger bridges of cyclic aliphatic and aromatic compounds (typically having more than 15 atoms) and fullerenes can be expected. The compound does not need to be limited to include only carbon atoms, and may include hetero I atoms such as N, S, O, P, and the like. Heteroatoms are best introduced with non-tetragonal bonding angle configurations, which in turn allow covalent attachment of arms 1 ^ -116 or R'rR at additional bonding angles. Regarding the expected substituents and derivatizations of cage compounds, it should be noted that many substituents and derivatizations are appropriate. For example, when caged compounds are fairly hydrophobic, hydrophilic substituents can be introduced to increase the solubility of the hydrophilic solvent and vice versa. Therefore, where polarity is desired, polar side groups can be added to the cage compound. It is further expected that appropriate substituents • 27 · 200408662 (21) may also include heat-labile groups as well as nucleophilic and electrophilic groups. It should also be noted that functional groups can be used in cage compounds (for example, to facilitate crosslinking reactions, derivatization reactions, etc.). When a cage compound is derived, the expected derivatization includes a cage compound function, and particularly preferred halogens are fluorine and bromine. When the thermosetting monomer (a) has an aryl group coupled to the arms R'i-R, as shown in Structure 2, the aryl group preferably contains a phenyl group, and the aryl group is more preferably a phenyl group to form hexaphenylene. In another aspect of the subject matter of the present invention, it is contemplated that various aryl compounds other than phenyl (or hexaphenylene) are also suitable, including substituted and unsubstituted di- and polycyclic aromatic hydrocarbon compounds. Substituted and unsubstituted di- and polycyclic aromatic hydrocarbon compounds are particularly preferred, and the increased thermosetting monomers are preferred. For example, pyrene, phenanthrene, and E are particularly expected when the substitution of an alternative aryl group by one factor over another factor is desired. In other cases, when it is desired that the alternative aryl groups extend symmetrically, polycyclic aryl groups such as coronabenzene are contemplated. In a particularly preferred aspect, the intended di- and polycyclic aromatic groups have a conjugated aromatic hydrocarbon system, which may or may not include heteroatoms. With regard to the substitution and derivation of the intended aryl group, the same considerations apply to cage compounds, as described herein. Regarding the arms and R '^ R'6, R "R6 is preferably each selected from the group consisting of aryl, branched aryl, and arylene ether, and preferably each selected from aryl, branched aryl, and arylene Ether without substitution. Particularly expected aryl groups for 1 ^ -116 and R'i-R'6 include those having (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and (benzene Ethynyl) phenyl group of phenylphenyl moiety. Particularly preferred arylene ethers include (phenylethynylphenyl) phenyl ethers. Aryl groups that are particularly expected for R7 include phenyl and substituted aryl groups such as hydrogen and alkane Aryl, aryl, or halo substituted phenyl. -28 · 200408662 (22) In another aspect of the subject matter of the present invention, suitable arms of the thermosetting component are not limited to aryl, branched aryl, and aryl Ether, as long as the replacement of the arms RrRs with R'-R, containing reactive groups, and thermosetting components includes reactions involving reactive groups. For example, the expected arms can be quite short without exceeding six Atoms, which may or may not be atoms. The short arms are particularly advantageous when voids or voids are desired to be added to the final product or material and the size of the voids Must be quite small. In contrast, when extra long arms are preferred, the arms may contain oligomers or polymers having 7-40 atoms and above. These long arms are smaller than The composition is more advantageous for material stability, thermal stability, or porosity. In addition, the length and chemical composition of the arms covalently coupled to the intended thermosetting monomer can be changed within one monomer. For example, cage compounds May have two rather short arms and two rather long arms to promote factorial growth in a particular direction during polymerization. In another example, the cage compound may have two arms that are chemically different from each other To promote regioselective derivatization. Although all arms in a thermosetting component preferably have at least one reactive group, in another aspect less than all arms must have one reactive group. For example The cage compound may have 4 arms, and only 3 or 2 arms carry a reactive group. Alternatively, the aryl group in the thermosetting component may have 3 arms, of which only 2 or 1 The arms have reactive groups -Generally, the number of each of the arms 1 ^ -116 and the number of reactive groups is expected to depend on the chemical properties of the arms and the quality of the desired end product. In addition, it is expected that the reactive groups are positioned in any of the arms Portions, including the main.bond side chains or terminals of the arms. Note that the number of reactive groups-29- 200408662 (23) in the thermosetting component (a) can be used as a tool to control the degree of crosslinking. For example, when required When the degree of crosslinking is relatively low, the desired thermosetting monomer may have only one or two reactive groups, which may or may not be located in one arm. On the other hand, when a relatively high degree of crosslinking is required, three Two or more reactive groups may be included in the monomer. Preferred reactive groups include electrophilic and nucleophilic groups. Better groups can participate in the cycloaddition reaction. Particularly preferred reactive groups are ethynyl groups. In addition to the reactive groups in the arms, other groups including functional groups can also be included in the arms. For example, after polymerization of a thermosetting monomer, when a special functionality (such as a heat-resistant portion) is suitably added to the polymer, the functionality can be covalently bonded to the functional group. The thermosetting component (a) can be polymerized by various mechanisms. The actual mechanism of polymerization depends mainly on the reactive groups involved in the polymerization process. Therefore, the expected mechanisms include nucleophilicity, electrophilicity, and aromatic hydrocarbon substitution. Use, addition, elimination, free radical polymerization, and cycloaddition, the most preferred polymerization mechanism is cycloaddition, which involves at least one Ethynyl with at least one arm. In the thermosetting component (a) having an arm selected from the group consisting of an aryl group, a branched chain aryl group, and an extended aryl ether, at least three of the aryl group, the branched chain aryl group, and the extended aryl ether have a single acetylene group, and the thermosetting property The polymerization of component (a) may include a cycloaddition reaction (ie, a chemical reaction) of at least two ethynyl groups. In another example, in a thermosetting component (a) in which all aryl, branched aryl, and arylene ether arms have a single ethynyl group, the polymerization process may include a cycloaddition reaction of ethynyl groups (ie, chemical reaction). In another example, a cycloaddition reaction (i.e., a Diels-Alder reaction) may occur between an ethynyl group in at least one arm in the thermosetting component (a) and a dienyl group located in the polymer. It can be further expected that the thermosetting group-30-200408662 (24) part (a) polymerization occurs when additional molecules (such as a cross-linking agent) are not involved, and is preferably used as a cycloaddition between the reactive groups of the thermosetting component (a)成 反应。 Reaction. However, in another aspect of the subject matter of the present invention, a crosslinking agent may be used to covalently couple the thermosetting component (a) to the polymer. This covalent coupling can occur between a reactive group and the polymer or between a functional group and the polymer. Depending on the mechanism of polymerization of the thermosetting component (a), the reaction conditions may vary considerably. For example, when the monomer is polymerized by a cycloaddition reaction using an ethynyl group using at least one arm, heating of the thermosetting monomer to about 250 ° C or more for about 45 minutes is usually sufficient. In contrast, when a monomer is polymerized by a radical reaction, it is suitable to add a radical starter. The preferred polymerization methods and techniques are described in the examples. The thermosetting component can be located at any point on the polymer or on the polymer backbone, including the polymer's terminal or side chains. The polymers are contemplated to include various polymer types such as polyimide, polystyrene, polyamidine, and the like. However, it is particularly expected that the polymer contains polyarylene, and more preferably poly (arylene ether). In a more preferred aspect, the polymer is made at least partially from a thermosetting monomer, and it is specifically expected that the polymer is made entirely from the isomers of the thermosetting component. In a particularly expected arm, the stretching technique is described in Figure 4, where Ad represents adamantane or adamantane group, and phenylacetylene is a starting molecule, which is reacted with TBPA (as above) (1) to obtain 1,3,5,7-H [374f- (phenylethynyl) phenyl] adamantane (TPEPA). Alternatively, phenylacetylene can be converted (2) to 4- (phenylethynyl) phenyl bromide, which is subsequently reacted (3) with trimethylsilylacetylene (TiMSA) to form 4- (phenylethynyl) ) Phenylacetylene. Then, 200408662 (25) butyl BPA can be reacted with 4- (phenylethynyl) phenylacetylene (4) to obtain 1,3,5,7-{{3 '/ 4'-[4 "-(phenyl Ethynyl) phenylethynyl] phenyl} adamantane (TPEPEPA). In another extension reaction, 4- (phenylethynyl) phenylacetylene / reacts with 1-bromo-4-iodobenzene (5) To form 4- [4f- (phenylethynyl) phenylethyl, alkynyl] phenyl bromide, which is further converted (6) to 4- [4f- (phenylethynyl) phenylethyl bulk] acetylene. Then, the 4- [4 '-(phenylethynyl) phenylethynyl] acetylene thus formed is reacted with TBA (7) to obtain 1,3,5,7- 肆 {374, [4Π- (4 "' -(Phenylethynyl) phenylethynyl) phenylethynyl] phenyl} adamantane.

The present invention also provides a spinning low dielectric constant polymer, comprising: (a) a polymer having a hanging cage structure-[〇R24 (R25) m〇R26] n-, wherein R24 is -C6H3-; R25 is adamantane, adamantane, (C6H5) p (adamantane) or (匸 6 仏)? (Adamantane); 111 = 1-3; 11 = 1-103;? = 0 or 1; and 1126 is a group of 2,3,4,5- (tetraphenyl) cyclodienone-1 or

And (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, and the first functionality may interact with a polymer having a hanging cage structure to be applied as a composition When reaching the substrate, the second functionality can interact with the substrate. The β adhesion promoter (b) is preferably selected from (i) polycarbosilane, (ii) silane, (iii) phenol-formaldehyde resin or oligomer, (Iv) glycidyl ether, (v) unsaturated carboxylic acid ester or (vi) the above-mentioned vinyl cyclic oligomer or -32-200408662 (26) polymer. As mentioned above, the present invention also provides a spinning low dielectric constant material, comprising: (a) a first main chain having a first aromatic hydrocarbon moiety and a first reactive group; having a second aromatic hydrocarbon moiety and a second reactivity A second main chain of the group, wherein the first and second main bonds are crosslinked by the first and second reactive groups in a crosslinking reaction; and covalently bonded to at least one of the first and second main chains A cage structure, wherein the cage structure includes at least 8 atoms; and (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, and the first functionality may be the same as that of the first One interacts with the second backbone and the second functionality can interact with the substrate when the composition is applied to the substrate. At least one of the main chains may contain poly (arylene ether), each having two hanging adamantyl groups as a cage structure, as shown in structure 3A-B (only one repeating unit of the main chain is shown). The preferred crosslinking conditions are heating the poly (arylene ether) backbone to a temperature of about 200-250 ° C or above for about 30-180 minutes. Structure 3B can be synthesized as outlined in Examples 1-3 below.

Structure 3 A Structure 3 B The first and second aromatic hydrocarbon portions contain a phenyl group, and the first and second reactive groups are ethynyl, tetracyclone, or ethynyl and tetracyclone portions, respectively, at- 33- 200408662

(27)

The Diels-Alder reaction reacts to crosslink the backbone. In another specific example, the main chain does not have to be limited to poly (arylene), but it may depend on the desired physical-chemical properties of the final low dielectric constant material. Therefore, when the Tpt is expected to be quite high, inorganic materials are particularly expected, including inorganic polymers containing silicate, (SiO2) and / or aluminate (Al203). Organic polymers can be expected in cases where flexibility, ease of processing, or low stress / TCE are required. Therefore, depending on the particular application, it is expected that the organic backbone includes aromatic polyimides, polyamidoamines, and polyesters. Although it is preferably done from a low molecular weight polymer having a molecular weight of about 1000 to 10,000, the chain lengths of the first and second polymerized main chains can be considered to vary between 5 or less repeating units to several 104 repeating units and above. The preferred main chain is synthesized from the monomers in an aromatic substitution reaction, and the synthetic route is shown using the examples of Figs. It is further contemplated that the alternative main chain may also be at least partially branched, hyperbranched, or crosslinked. Alternatively, the backbone can be synthesized in situ from the monomers. Suitable monomers may preferably include aromatic bisphenol compounds and difluoroaromatic compounds, which may have between 0 and about 20 built-in cage structures. It is also expected that a suitable thermosetting component (a) may have or include a quadrangular junction ® structure, which is 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, and at least two of the side chains Ri-116 include an aromatic hydrocarbon moiety and a reactive group, wherein at least two of the reactive groups of the first monomer One or more of the reactive groups of the second monomer react to produce a low dielectric constant polymer. In the general structure 4A, a cage structure, preferably an adamantane, is coupled to the four aromatic hydrocarbon moieties participating in the polymerization, wherein Ri-Re may be the same or different. Ri, R2, R3, and R4 up to • 34- 200408662 (28) At least one contains at least two isomers. In the general structure 4B, each cage structure, preferably adamantane, is coupled to three aromatic hydrocarbon moieties participating in the polymerization, wherein RrR6 may be the same or different and at least two of these cage compounds are aryl groups. Or through a substituted aryl group. At least one of Ri, R2, R4, and R6 contains at least two isomers. Preferably, at least two isomers of adamantane are present relative to r7.

Structure 4A Structure 4B When a monomer with a quadrangular structure is used, the cage structure covalently connects the four main chains in a three-dimensional configuration. A typical monomer with a quadrangular structure and its synthesis is shown in Figure 3A. It is further noted that the alternative monomers need not be limited to compounds having substituted or unsubstituted adamantane as a cage structure, but may also include any cycloalkyl or cycloalkylene structure, cubic alkane, substituted or unselected Substituted amalgam or fullerene as a cage structure. It is contemplated that the substituents include alkyl, aryl, autogen, and functional groups. For example, adamantane can be substituted with a -CF3 group, a third alkyl group having 1 to 10 carbon atoms, phenyl, -COOH, -NO24-F, -C1, or -Bι :. Therefore, depending on the chemical properties of the cage structure, each number other than the four aromatic part may be attached to the cage structure. For example, when a relatively low degree of cross-linking through a cage structure is desired, 1 to 3 aromatic hydrocarbon moieties can be attached to the cage structure, of which the aromatic hydrocarbon moiety is -35 · 200408662

(29) It may or may not contain a reactive group for crosslinking. Where a higher degree of crosslinking is preferred, 4 or more aromatic hydrocarbon moieties may be attached to the cage structure, where all or almost all of the aromatic hydrocarbon moieties carry one or more than one anti /

Responsive group. In addition, it is expected that the aromatic hydrocarbon moiety attached to the center ridge structure may support other cage structures, where the ridge structure may be the same as the center cage structure, or may be completely different. For example, it is contemplated that the monomer may have a fullerene cage structure to provide a relatively high number of aromatics and adamantane within the aromatics. Therefore, it is expected that the cage structure can be covalently bonded to the first and second main chains or more than two main chains. With regard to the chemical nature of the aromatic hydrocarbon moiety, it is expected that a suitable aromatic hydrocarbon moiety contains a phenyl group, more preferably a phenyl group and a reactive group. For example, the aromatic moiety may comprise a diphenylacetylene or (phenylethynylphenyl) group or a substituted diphenylacetylene, wherein the substituted diphenylacetylene may include double bonds covalently through carbon-carbon bonds or carbon-non-carbon bonds Additional phenyl groups bonded to diphenylacetylene and ethynyl, ether, ketone or ester groups.

Monomers with hanging cage structures are also contemplated, as shown in the example of Figure 7, where two adamantane are used as hanging groups. However, it should be noted that the hanging cage structure is not limited to two augustane structures. It is expected that alternative cage structures I include single and multiple substituted adamantyl, adamantane and fullerenes in any chemically sound combination. Where special solubility, oxidative stability, or other physical-chemical properties are desired, substitution can be introduced into the cage structure. Therefore, the expected substitutions include halogen, alkyl, aryl, and alkenyl, but also functional and polar groups, including esters, acidic, nitro, and amine groups. It should also be noted that the main chains need not be the same. In some aspects of the alternative specific example, -36- 200408662 (30) may benefit from two or more chemically different main chains to produce a low dielectric constant material, as long as the alternative low dielectric constant material includes an aromatic portion The first and second main chains, reactive groups, and cage-like compounds covalently bonded to the main chain are sufficient. As for the reactive group, it is expected that reactive groups other than the ethynyl group and the tetracyclic snapper group can be used, as long as the alternative reactive group can crosslink the first and second main chains without using an external crosslinking agent. For example, suitable reactive groups include benzocyclobutenyl. In another example, the first reactive group may include an electrophile and the second reactive group may include a nucleophile. It is further expected that the number of reactive groups depends mainly on (a) the reactivity of the first and second reactive groups, (b) the cross-linking strength between the first and second main chains, and (c) within the low dielectric material. Depends on the desired degree of crosslinking. For example, when the first and second reactive groups are sterically hindered (eg, ethynyl between two derivatized phenyl rings), a significant number of reactive groups are required to crosslink the two main chains to a certain Kind of degree. Also, when a relatively weak bond such as a hydrogen bond or an ionic bond is formed between the reactive groups, a considerable majority of the reactive groups are required in order to achieve stable crosslinking. In the case where a reactive group in one main chain can react with the same reactive group in another main chain, only one kind of reactive group is required. For example, ethynyl groups on the same two different backbones can react in addition and cycloaddition reactions to form crosslinked structures. It should also be noted that the number of reactive groups can affect the ratio of intermolecular to intramolecular cross-linking. For example, relatively high concentrations of reactive groups in the first and second backbones will facilitate intramolecular reactions at relatively low concentrations in the two backbones. Similarly, the relatively low concentration of reactive groups in the first and second backbones will facilitate intermolecular reactions at the relatively high concentrations of the two main chains. The balance of intra- and inter-molecular reactions is also affected by the distribution of different reactive groups between the main chains. When an intermolecular reaction is desired, one reactive group may be placed on the first main chain and the other reactive group may be placed on the second main chain. In addition, when sequential crosslinking under different conditions (for example, two different temperatures) is desired, additional third and fourth reactive groups may be used. However, the reactive end of the reactive group of the preferred backbone in the addition reaction depends on the chemical nature of the alternative reactive group, and many other reactions are also contemplated, including nucleophilic and electrophilic substitution or elimination Effect, free radical reaction, etc. In addition, alternative reactions may also include the formation of non-covalent bonds such as electrostatic, ion, and hydrogen bonds. Therefore, cross-linking of the first and second main chains occurs by forming covalent or non-covalent bonds between the same or different reactive groups which may be positioned on the same or two main chains. In another aspect of the alternative embodiment, the cage structure may include a structure other than adamantane including adamantane, bridging crown ether, cubic or fullerene, as long as the alternative cage structure has at least 8 atoms is enough. The choice of the appropriate cage structure is determined by the desired space requirement of the cage structure. When a relatively small cage-like structure is preferred, a single adamantane or adamantane group is sufficient. It is expected that the structure of the main chain including adamantane and auryl alkyl groups is shown in Figs. 8A and 8B. The large cage structure may contain fullerenes. It should also be noted that the alternative main chain need not be limited to a single cage structure. Appropriate ridge notes may include two or five cage structures or other molecules with more distinct cage structures. For example, fullerenes can be added to one or both ends of the polymerized main chain, while gold steel alkyl groups are placed in other parts of the main chain. Derivatives of -38- 200408662 (32) or multiple cage structures are also expected, including oligomeric and polymeric cage structures, of which larger cage structures are desired. The chemical composition of the cage structure need not be limited to carbon atoms, it is to be noted that alternative cage structures may have / atoms (ie, heteroatoms) other than carbon atoms, whereby it is expected that the heteroatoms may include N, 0, P, S, B,-etc. Regarding the position of the cage structure, it is expected that the cage structure may be connected to the main chain at various positions. For example, when it is desired to mask terminal functional groups in the main chain or stop the polymerization reaction that forms the main chain, a cage structure can be used as an end cap. The typical structure of the end cap is shown in Figures 9A and 9B. In other cases where a large number of cage structures are desired, the cage structure is expected to be a hanging structure covalently connected to the main chain. The location of the covalent linkage can vary, depending on the amount of chemical replenishment of the backbone and the cage structure. Therefore, a proper covalent connection would involve connecting molecules or functional groups, while other connections may be single or double bonds. When the cage group is a hanging group, it is particularly expected that more than one backbone can be attached to the cage structure. For example, a single cage structure can be linked to at least two or three or more backbones. Alternatively, it is contemplated that the cage group may be an integral part of the main chain.

Turning now to FIG. 10, a typical polymer is shown, in which the first main chain 10 is crosslinked by the first reactive group G15 and the second reactive group G25 to the second main chain 20 by I, where the cross-linking results in Price key 50. Each of the two main chains has at least one aromatic moiety (not shown). A plurality of hanging cage structures 30 are covalently bonded to the first and second main chains, and the first main chain 10 further has a terminal fluorene group 32. At least one of the terminal cage group 32 and the hanging-cage structure 30 carries at least one substituent R (40), wherein the substituent 40 may be a halogen, an alkyl group, or an aryl group. The cage structures each contain at least 8 atoms. -39- 200408662

(33) Adhesion promoter (b): One of the adhesion promoters is formula (R18) f (R19) gSi (R2Q) h (R2i) # silane, among them! ^ 8 'Rm'Rm and RZ1 each independently represent hydrogen, a hydroxyl group, an unsaturated or saturated' group, a substituted or unsubstituted dry group, wherein the substituent is an amine group or an epoxy group, and the · group is an unsaturated or saturated alkyl group. Oxy, unsaturated or saturated carboxylic acid group or aryl group, in which at least two of R1S 'Rw' Rzo and Rzl represent hydrogen, meridian, saturated or unsaturated alkoxy, unsaturated alkyl or unsaturated carboxylic acid group ; And f + g + h + I S4. Examples include ethylene silanes such as H2OCHSi (CH3) 2H and H2C = CHSi (R27) 3 where R "is CH3〇, C2H50, AcO, H2C = CH, or H2C = LuC (CH3) 〇-, or ethylene Phenylfluorenylsilane; formula H2C = CHCH2_Si (OC2H5) 3 and H2C = CHCHrSi (H) (OCH3) 2; allylsilane; glycidyloxypropyl silane such as (3-glycidyloxypropyl) Diethoxysilane and (3-glycidyloxypropyl) trimethoxysilane; methacryloxypropylsilane of the formula h2o (ch3) co0 (CH2) 3-Si (〇R28) 3, where r28 is alkyl ', preferably methyl or ethyl; aminopropylsilane derivatives, including H2N (CH2) 3Si (〇CH2CH3) 3, H2N (CH2) 3Si (OH) 3, or H2N (CH2) 3 〇C (CH3) 2CH = CHSi (〇CH3) 3. The above stone yaki is commercially available from Gelest. Another adhesion promotion product is the formula-[R22C6H2 (〇H) (R23)] j- Benzene-formaldehyde resin or oligomer, where r22 is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl; R23 is alkyl, alkyl / alkyl, alkyl Ethyl, cycloalkylene, allylic, or aryl; and j = 3-100. 4 Examples of useful alkyl groups include-CH2 -And- (CH2) k-, where k > 1. Particularly useful phenol-formaldehyde resins or oligomers have a molecular weight of 1500 and are commercially available from -40-200408662 (34)

Schenectady International. Another useful adhesion promoter is glycidyl ether, including, but not limited to, 1,1, pshen- (hydroxyphenyl) ethane triglycidyl ether, commercially available from TriQuest.

Another useful adhesion promoter is an unsaturated carboxylic acid ester containing at least one carboxylic acid group. Examples include trifunctional methacrylate, trifunctional acrylate, trihydroxymethylpropane triacrylate, dipentaerythritol pentaacrylate, and glycidyl methylpropionate. The above are commercially available from Sartomer. Another useful adhesion promoter is an ethylene-based cyclic pyridine oligomer or polymer, where the cyclic group is a p-pyridine, aromatic or heteroaromatic hydrocarbon. Useful examples include, but are not limited to, 2-vinylpyridine and 4-vinylpyridine, commercially available from Reilly; ethylene aromatic hydrocarbons; and ethylene heteroaromatics including, but not limited to, ethylene quinoline and ethylene carba. Sit, Yijun Weijun and Yigui *. No. σ sat.

A preferred adhesion promoter (b) is polycarbosilane, which is disclosed in the Common Assignment US Patent Application Serial No. 09/471299, filed on December 23, 1999, all of which are incorporated herein by reference. Polycarbosilane is of formula (I): Η I Si- R9 r8- a R10 -Si—

Rn b 〒12 Si-R14-〇-R13

Rl5Si —Rl7 · r16 d where Rs, R14 and R17 each independently represent a substituted or unsubstituted alkylene, cycloalkylene, ethylene, naphthyl, allylic or aryl; R9, R1 ( ), Rn, -41-200408662

(35) R12, R15, and R16 each independently represent a hydrogen atom or an organic group including an alkyl group, an alkylene group, a vinyl group, a cycloalkyl group, an allyl group, or an aryl group, and may be linear or branched; R i 3 Represents organic crushed, crushed alkoxy, crushed oxy or organic groups; and a, b, 'c and d meet the conditions of [4 < a + b + c + dS 100,000], and b and c and d may be common Or 'independently zero. Organic groups can contain up to 18 carbon atoms but typically contain about 1 to about 10 carbon atoms. Useful alkyl groups include -CH2- and-(CH2) e-, where e> l. The preferred polycarbosilanes of the present invention include dihydropolycarbosilanes, where Rs represents a substituted or unsubstituted alkylene or phenyl group, the R9 group is a hydrogen atom and there are no auxiliary groups in the polycarbosilane chain; that is, b , C and d are all zero. Another preferred polycarbosilyl group is such a group, wherein the R9, R10, Ru, R12, R15 and R16 groups of the formula (I) are substituted or unsubstituted groups having 2 to 10 carbon atoms. base. The alkenyl group may be a vinyl group, a propenyl group, an amidino group, a butenyl group, or any unsaturated organic backbone group having up to 10 atoms. The hooves may be dienyl in nature and include unsaturated alkenyl groups attached or substituted on the main chain of different alkyl or unsaturated organic polymers. Examples of such preferred polycarbosilanes include dihydro or alkenyl-substituted polycarbosilanes such as polydihydrocarbon silanes, polyallyl hydrocarbon silanes, and polydihydrocarbon silanes and polyallylhydrocarbon silanes. Tactic copolymer. ® In a more preferred polycarbosilane, the R9 group of Formula 1 is a hydrogen atom and R8 is a methylene group, and the subsidiary groups b, C, and d are zero. Other preferred polycarbosilane compounds of the present invention are polycarbosilanes of formula 1, wherein R9 and R15 are hydrogen and 118 and r17 are methylene, R16 is alkenyl and the subsidiary groups b and c are zero. Polycarbosilanes can be prepared from prior art / technology or provided by manufacturers of polycarbosilane compositions. In the best polycarbosilanes, the R9 group of formula (I) is a hydrogen atom and Rs is -CH2-; the subgroups b, c and d = 0 and a = 5-25. These best-in-class Shi Xi Yuans are available from Starfire Systems. -42. 200408662

(36) Specific examples of these optimal polycarbosilanes are as follows: polycarbosilane weight average molecular weight polydispersity acuity molecular weight (Mp) 1 400-1,400 2-2.5 330-500 2 330 1.14 320 3 (with 10% olefin (Propyl) 10,000-14,000 10.4-16 1160 4 (with 75% allyl) 2,400 3.7 410 It can be known from the formula (I) that the polycarbosilane used in the present invention, when c > 0, may contain a form of broken oxygen. Oxidizing group. Therefore, when c > 0, Rn represents an organic group, a silyl group, a siloxy group, or an organic group. It should be noted that the oxidized part Cc of the polycarbosilane is effective within the scope of the present invention. It can also be known that c can be 0 and has nothing to do with a, b, and d. The only condition is that the groups a, b, c, and d of the polycarbosilane of formula 1 must meet [4 < a + b + c + d < 100,000]. Conditions, and b and c may be zero together or independently. The polycarbosilane of the present invention is preferably added in a slightly effective amount of about 0.5% to 20% based on the weight of the thermosetting composition (a) of the present invention, and usually more preferably in an amount of up to about 5.0% by weight of the composition. Polycarbosilanes can be made from raw materials currently available from many manufacturers and using conventional polymerization methods. Regarding the example of the synthesis of polycarbosilane, the raw material may be a common organic silane compound or a self-polymer silane as a raw material, by heating a blend of polysilane and polyborosiloxane! To produce the corresponding polymer within the air pressure, or by heating the blend of polysilane and low molecular weight carbosilane in an inert gas pressure, or by heating the blend of polysilane and low molecular weight carbosilane to the inert gas pressure. It is produced in the presence of a catalyst such as polyborodiphenylsiloxane to produce a corresponding polymer. Polycarbosilanes can also be synthesized by Grinard reaction -43 · 200408662 (37), which is recorded in US Patent No. 5,153,295, which is incorporated herein by reference. By combining the preferred polycarbosilane with the thermosetting component (a) or the polymer and subjecting the composition to heat or high energy, the resulting composition has excellent adhesive properties throughout the entire polymer, and can ensure that any coating film contacting the surface Affinity. The hair * Ming polycarbosilane can also improve the streak control, viscosity and film uniformity. Visual inspection confirmed the existence of improved streak control. The composition of the present invention may also contain additional components such as additional adhesion promoters, anti-foaming agents, detergents, flame retardants, pigments, plasticizers, stabilizers and surfactants. Practicality The composition of the thermosetting component (a) and the adhesion promoter (b) of the present invention can be combined with other specific additives to obtain specific results. Representative examples of this additive are metal-containing compounds such as magnetic particles, for example, barium ferrite, barium oxide, if necessary in a mixture with cobalt, or other metal-containing particles, for magnetic media, optical media or other records Media; conductive particles such as metal or carbon used as conductive sealants; conductive adhesives; conductive coatings; electromagnetic interference (EMI) / radio frequency (RFI) shielding coatings; static dissipatives; and electrical contacts. When using these additives, the composition of the present invention can be used as an adhesive β. The composition of the present invention can also provide protection to the environment for manufacturing, storage or use, such as a coating film for metals, semiconductors, capacitors, inductors, Conductors, solar cells, glass and glass fibers, quartz and quartz fibers provide surface passivation. The composition of the thermosetting component (a) and the adhesion promoter (b) of the present invention can also be used in gaskets and gaskets, preferably as a layer of gaskets or gaskets, such as wrapping gauze, or can be used alone. In addition, the composition can also be used in antifouling coating films, -44-200408662 (38) for objects such as ship parts; electrical switch coverings; bathtub and bonnet coating films; in mold resistant coating films; or to provide resistance to objects Flammability, weather resistance or water resistance. Due to the temperature resistance range of the composition of the present invention, the composition of the present invention can be coated on low-temperature containers, autoclaves, and furnaces, as well as on heat exchange and other heated or cooled surfaces, and on objects exposed to microwave radiation. The composition of the thermosetting component (a) and the adhesion promoter (b) of the present invention may also be a dielectric material. The dielectric material preferably has a dielectric constant k of less than 3.0. The composition layer of the thermosetting component (a) and the adhesion promoter (b) of the present invention can be formed by solution technology such as spraying, rolling, dripping, spin coating, flow coating, or casting. Coated better. The composition of the present invention is preferably dissolved in a solvent. Suitable solvents for the solution of the composition of the invention include any pure organic, organometallic or inorganic molecules or mixtures thereof that are volatile at the desired temperature. Suitable solvents include aprotic solvents, for example, cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone; cyclic amines such as N-alkylpyrrolidone, in which the alkyl group has about 1 to 4 Carbon atom; with N-cyclohexylpyrrolidone and mixtures thereof. Other organic solvents can also be used, as long as it can help the dissolution of the adhesion promoter and can effectively control the viscosity of the resulting solution as a coating solution. Various convenient measures such as stirring and / or heating can be used to help dissolve. Other suitable solvents include methyl ethyl ketone, fluorenyl isobutyl ketone, dibutyl ether, cyclic difluorenyl polysiloxane, butyrolactone, 7-butyrolactone, 2-heptanone, 3-ethyl Ethyl oxypropionate, polyethylene glycol ether, polypropylene glycol methyl ether, acetate, mesitylene, phenyl ether and hydrocarbon solvents such as xylene, benzene and toluene. A preferred solvent is cyclohexanone. Generally, the layer thickness is between 0.1 to about 15 microns. As a microelectronic dielectric interlayer, the layer thickness is usually less than -45-200408662 (39) 2 microns. The composition of the thermosetting component (a) with the adhesion promoter (b) and the solvent is preferably treated at a temperature of about 30 to about 350 ° C for about 0.5 to about 60 hours. This treatment usually forms oligomers of thermosetting component (a) and adhesion promoter (b), as demonstrated by GPC. The composition of the present invention can be used in electrical devices, in particular, as an interlayer dielectric in interconnects associated with a single integrated circuit ("ICn) wafer. Integrated circuit wafers typically have several layers of the present invention on their surface And multilayer metal conductors. It can also include areas of the composition of the invention between different metal conductors or areas of the conductors within the same layer or layer of the integrated circuit. In the application of the polymers of the invention to ICs, the combination of the invention The solution of the substrate is applied to a semiconductor wafer using a conventional wet coating method such as spin coating; in certain cases, other conventional coating technologies such as spray coating or flow coating may also be used. As an example, cyclohexanone of the composition of the present invention The solution is spin-coated on a substrate containing a conductive component therein, and then the coated substrate is subjected to thermal processing. A typical formulation of the composition of the present invention is strictly in accordance with the operating conditions under ambient conditions to prevent any traditional Trace metal contamination in a device with a non-metallic substrate is prepared by dissolving the composition of the present invention in a cyclohexanone solvent. The resulting solution, based on the total solution weight, preferably contains 1 to about 50% by weight of the thermosetting component (a) and the adhesion promoter (b) and about 50 to about 99% by weight of the solvent, more preferably about 3 to about 20% by weight of the thermosetting component (a) and the adhesion promoter ( b) and about 80 to about 97% by weight solvent.-The application of the present invention is exemplified as follows. The application of the composition of the present invention to form a layer on a flat or terrain surface or substrate can be made by using any conventional device. 46- 200408662 ( 40) It is best implemented by a spin coater because the composition here has a controlled viscosity suitable for the applicator. Evaporation of the solvent can be by any suitable means, such as simple air drying during spin coating and exposure to the surroundings Environment or heating / heating up to 350 ° C. The substrate may have at least two layers of the composition of the present invention with a thermosetting component (a) and an adhesion / promoter (b). The substrates contemplated herein may include any Desirable substantially solid materials. Special substrate layers include thin films, glass, ceramics, plastics, metals or coated metals or composite metals. In preferred embodiments, the substrate includes silicon or gallium arsenide grains or wafers Surface, packaging surface if found in copper, Silver, nickel, or gold-plated lead frames, with copper surfaces found on circuit board or packaging interconnect traces, via walls, or reinforced interfaces ("copper" includes consideration of bare copper and its oxides), polymer-based packaging or board interfaces If found on a polyimide-based curved package, the surface of lead or other metal alloy solder balls, glass, and polymers. In a more specific example, the substrate includes materials commonly used in the packaging and circuit board industries such as silicon, copper, glass, and Polymer. The composition of the present invention can also be used as a dielectric substrate for microchips, multi-chip modules, laminated circuit boards or printed wiring boards. A circuit board composed of the composition of the present invention can be mounted on its surface pattern For various conductive circuits. The circuit board can include various reinforcements such as woven non-conductive fibers or glass cloth. The circuit board can be one-sided and two-sided. The layer made of the composition of the invention has a low dielectric constant and high heat. Stability, high mechanical strength and the surface of electronic substrates include silicon, silicon nitride, oxide: silicon, oxygen-containing silicon carbide, silicon dioxide, silicon carbide, silicon-oxynitride, nitride, "Nitride, Nitriding , Ming, copper, Zhao, organic oxygen bite embankment, excellent adhesion and - a fluorinated organic silicon cullet glass. Because the adhesion promoter is molecular -47- 200408662

(41) type dispersion, so these layers proved to have excellent adhesion to all fixed surfaces including the substrate and above the cap or cover layer such as 3 〇 02 and Si3N4 cap layer. The use of these layers eliminates the need for additional processing steps to be applied with at least one primer to achieve film adhesion to the substrate and / or covering surface. After the application of the electronic terrain-forming substrate according to the present invention, the coated structure is subjected to baking and curing thermal methods to polymerize the coating film at an increased temperature range of about 50 ° C to about 450 ° C. The curing temperature is at least about 300 ° C because lower temperatures are not sufficient to complete the reaction. Generally, curing is preferably performed at a temperature of about 375 ° C to about 425 ° C. Curing can be carried out in traditional curing chambers such as electric furnaces, heating plates, etc., and is usually carried out in an inert (non-oxidizing) gas pressure (nitrogen) in the curing chamber. Any non-oxidizing or reduced gas calendar: (eg, argon, helium, hydrogen, and nitrogen process gases) can be used to implement the invention if it is effective to cure the silicone-modified thermosetting component (a) or polymer of the invention to This low-k dielectric layer is achieved. Although not to be construed as limiting, it is speculated that the thermal processing of the low dielectric constant composition of the present invention results in a crosslinked network of the thermosetting component (a) and the adhesion promoter (b). Basically, the thermal processing of the composition of the present invention results in the conversion of the silane portion of the preferred polycarbosilane adhesion promoter (b) to a methylenesilyl / fluorenylsilyl group, which is then unsaturated with the thermosetting component (a). It reacts with the surface of the substrate to generate a chemically bonded adhesion interface for the main thermosetting monomer (a) precursor. Such arylene / silyl groups are available throughout the composition as a source of attachment to borrow The chemical bond fastens and secures the interface surface of any contact. This reaction can also occur during the formulation or processing before the layer is formed. As shown, the dispersion of this free radical throughout the composition is considered to be an excellent adhesion of this layer to the surface of the underlying substrate and to cover surface structures such as a capping or covering layer. Materials shown in this article -48-200408662

(42) A very important finding is that the preferred polycarbosilane adhesion promoter of formula 1 has reactive hydrogen-substituted silicon in the polycarbosilane main chain structure. The characteristics of this polycarbosilane include: (1) reacting with the thermosetting component (a) and; (2) producing a thermosetting component modified with a polycarbosilane (a), which has improved adhesion properties. The resulting layer has a low dielectric constant k, which is defined herein as 3.0 or below. These layers demonstrate good adhesion to planar or topographic semiconductor surfaces or substrates. As shown previously, the polycarbosilane modified thermosetting component (a) or polymer coating film of the present invention can be used as an interlayer and covered with other coating films, for example, other dielectric (Si02) coating films, Si 〇2 & quality ceramic oxide layer, silicon-containing coating film, silicon-carbon coating film, silicon-nitrogen coating film, silicon-nitrogen-carbon coating film, diamond-like carbon coating film, titanium nitride, tantalum nitride, Tungsten nitride, aluminum, copper, buttons, organosilicon, organosilicon glass and fluorinated silica glass. This multilayer coating film is taught in U.S. Patent 4,973,526, which is incorporated herein by reference. As fully confirmed before, the polycarbosilane-modified thermosetting component (a) of the present invention prepared by this method can be easily formed as an inter-line dielectric layer between adjacent conductor paths on a manufactured electronic or semiconductor substrate. The film of the present invention can be used for copper double corrugation processing or substrate metal (such as aluminum) processing for the production of integrated circuit. The composition of the present invention can be used for spin-stacked films as desired, as disclosed in Michael E. Thomas, spin-packed films of π low-keff dielectric, Solid State Technology f 200 1 July), all of which are incorporated herein by reference reference. Examples Analytical test method: Proton NMR: Put 2-5 mg of sample material to be analyzed into NMR tube -49- 200408662 (43). Add about 0.7 ml of deuterated chloroform. Shake the mixture by hand to dissolve the material. The samples were then analyzed using Varian 400 MHz NMR. High Decade Energy Liquid Chromatography (HPLC): HPLC using a Phenomenex lima phenyl-hexyl 250x4.6 mm column. The column temperature was set at 40 ° C. Water and acetonitrile were used to improve spike separation. Time Yong Acetonitrile Initial 20% 80% 10 minutes 0% 100% 30 minutes 0% 100% The following experimental conditions were used: Injection volume 10 μl Detection UV at 200 μm Stop time 30 minutes After 5 minutes Sample preparation is as follows. Regarding the mixture of dentified intermediates, such as Example 5 of 1,3,5,7-Ci (3 / 4-bromophenyl) adamantane and 1,3 / 4-bis [lf, 3f, 5, and (3π / 4 ''-bromophenyl) adamantyl] benzene, shake the reaction mixture (0.5-1 ml) with approximately 4% HC1 (several ml). The organic layer was shaken with water. A sample of the organic layer (20 µl) was taken and acetonitrile (1 ml) was added. A mixture of the final products is shown in Example 5 of 1,3,5,7-[[Small- (phenylethynyl) phenyl] adamantane and 1,3 / 4-bis {Γ, 3 *, 5 ' -Refer to [3 " / 4 ''-(phenylethynyl) phenyl] adamantyl}. A mixture of benzene, mixed with chloroform (5 ml) and 3-5% ... HC1 (5 ml) reaction mixture (0.5 G) and shake it. Wash with water at -50- 200408662 (44). A sample of the organic layer (100 μl) was added to tetrahydroanil (0.9 mL). Gel Permeation Chromatography (GPC): GPC analysis system uses Water 717 plus Autosampler, Waters in-line degasser, Waters 515 HPLC ^, Waters 410 differential refractometer (RI detector) and two columns. Water PI liquid chromatography system composed of HP PI gel 5μ MIXED D was completed. The analysis conditions are: mobile phase tetrahydrofuran (THF) column flow (ml / min) 1.0 column temperature (° c) 40.0 detection of refractive index, polarity negative analysis running time 25 minutes injection volume (microliter) 50 sample (10 mg ) Prepared by adding tetrahydrofuran (1 ml). Mass Spectroscopy (MS): This analysis was performed on a Finnigan / MAT TSQ7000 three-stage quadrupole mass spectrometer system with an atmospheric pressure ionization (API) interface unit using a Hewlett-Packard series 1050 HPLC system as the analytical inlet. Mass ion current and variable single-wavelength UV data can be obtained for time-bit intensity chromatography. Chromatography was performed on a Phenomenex Luna 5 micron phenylhexyl column (250 x 4.6 mm). Samples are automatically injected with 10 or 20 microliters of concentrated solution in tetrahydrofuran and without tetrahydrofuran. The mobile phase flowing through the column was 1.0 microliters / minute acetonitrile / water, initially 70/30 for 5 minutes, and then planned to 100% acetonitrile in 15 minutes and maintained until 100 minutes (longer than the column completely Elution material is actually required). The atmospheric pressure chemical ionization (APCI) mass spectrum was recorded alternately in positive and negative modes. APCI corona discharge is 5 microamperes, right • 51 · 200408662

(45) Positive ionization is about 5 kV and negative ionization is about 4 kV. The heated capillary wire was kept at 200 ° C and the evaporator chamber was at 400 ° C. After the quadrupole mass analysis, a 15 kV variable frequency multiplication electrode and a 1500 volt electron multiplication voltage were set on the detection system. Mass spectrum is usually 0.5 sec / scan, about m / z 150 to 2000 amu for positive charge ionization and about m / z 125 to 2000 amu for negative charge ionization mode 0 Differential Scanning Card Meter (DSC): using TA instrument 2920 The differential scanning card meter, together with the controller and related software, performs DSC measurements. Standard DSC units with a temperature of 250 ° C to 725 ° C (inert gas pressure: 50 ml / min nitrogen) are used for analysis. Liquid nitrogen is used as a cooling gas source. A small amount of sample (10-12 mg) was carefully weighed into an Auto DSC aluminum sample pan (part # 990999-901) and an analytical balancer with an accuracy of 0.0001 g of spoon and a Mettler Toledo was used. The sample was sealed by covering the tray with a lid that was previously perforated in the center to allow gas to escape. The sample was heated from (TC to 450 ° C (cycle 1) at a rate of 100 ° C / min under nitrogen and then cooled to 0 ° C at a rate of 10CTC / min. The second cycle was directly at a rate of 100 ° C Run from 0 ° C to 450 ° C per minute (repeat cycle 1). Cross-linking temperature is determined from the first cycle. FTIR analysis: FTIR spectra were obtained in transfer mode using a Nicolet Magna 550 FTIR spectrometer. On uncoated substrates The background spectrum of the substrate is obtained on the substrate. The thin film spectrum is obtained using the substrate as the background. Then, the peak position and intensity change of the thin film are analyzed. Dielectric constant: The dielectric constant is obtained by coating an aluminum film on the f · curved layer, and then at 1 Capacitance-voltage measurement is performed at MHz and is determined by calculating the k value based on the layer thickness. Glass Koreanization Temperature (Tg): The glass transition temperature of the film is determined by measuring the film 200408662

(46) Stress is determined as a function of temperature. Film stress measurements were performed on a KLA 3220 Flexus. Before the thin film measurement, the uncoated wafer is annealed at 500 ° C for 60 minutes to prevent any errors due to the stress relaxation of the wafer itself. The wafer is then deposited with the material to be tested and processed through all required processing steps. The wafer is then placed in a stress meter, which measures the bow of the wafer as a function of temperature. The instrument calculates the stress vs. temperature curve, but the limitation is that the wafer thickness and film thickness are known. The results are displayed in the form of a graph. In order to determine the value of g, a horizontal tangent line is drawn (the slope of 0 on the stress versus temperature curve). The Tg value is where the graph crosses the horizontal tangent. It should be noted that if Ding g is determined after the first temperature cycle or subsequent cycles, the highest temperature is used because the measurement process itself will affect Tg. Isothermal Gravimetric Analysis (HTGA) Weight Loss Rate: The total weight loss rate is measured on the TA Instrument 2950 Thermogravimetric Analyzer together with the TA Instrument Thermal Analysis Controller and related models. Uses a Piatinel thermocouple and a standard furnace with a temperature range of 25 ° C to 1000 ° C and a heating rate of o.rc to 100 ° C / min. Small samples (7 to 12 mg) are weighed on a TGA balancer (resolution: 0.1? G; accuracy: = to ± 0.1%) and heated on a molybdenum pan. The sample was heated under nitrogen at a purge rate of 100 ml / min (60 ml / min on the furnace and 40 ml / min on the balancer). The sample was equilibrated under nitrogen at 20 ° C for 20 minutes, then the temperature was raised to 200 ° C at a rate of 10 ° C / minute and held at 200 ° C for 10 minutes. The temperature was then raised to 425 ° C at a rate of 10 ° C / min and held at 425 ° C for 4 hours. Calculate the weight loss rate during 4 hours at 425 ° C. Shrinkage: Film shrinkage is determined by measuring the film thickness before and after the process. The shrinkage ratio is expressed in% of the initial film thickness. When the film thickness is reduced, the shrinkage is positive. 〇3- 200408662

(47) The actual thickness measurement system is used. 八. ^^ 〇〇11 & 1111 ^ -88Spectral ellipsometry is performed as needed. The Cauchy model was used to calculate optimal values for Psi and Delta (details of the ellipsometry method are disclosed in, for example, "Spectral Ellipsometer Method and Reflectometry", H.G. Thompkins and William A. McGahan, John Wiley and Sons, Inc., 1999).

Emissivity index: The measurement of the emissivity index was performed together with the thickness measurement using a J.A. Woollam M-88 spectroscopic ellipsometer. Cauchy models were used to calculate the optimal values for Psi and Delta. Unless otherwise specified, the refractive index is recorded at a wavelength of 633 nm (details of the ellipsometry are disclosed in, for example, "Spectral Ellipsometer and Reflectometry", HGThompkins and William A. McGahan, John Wiley and Sons, Inc ·, 1999) 0

Modulus and hardness: Determine the modulus and hardness using an instrumented indentation test. This measurement was performed using MTS Nanoindenter XP (MTS Systems Corp., Oak Ridge, TN). Specifically, continuous stiffness measurement can be used to have accurate and continuous measurements of modulus and hardness rather than different values of the self-unloading curve. The system was calibrated with fused silicon with a nominal modulus of 72 + -3.5Gpa. The modulus of the fused silicon is obtained from the average value between 500 and 1000 nanometers of indentation depth. For thin films, the modulus and hardness values are obtained from the minimum value of the modulus versus depth curve, which is usually between 5 and 15% of the film thickness. Tape test: The tape test was performed according to the instruction manual provided by ASTM D3359-95. The grid is engraved into the dielectric layer according to the following. Perform tape test on the grid mark in the following ways: (1) a tape, preferably Scotch brand # 3m 600- 1 / 2x1296, placed on this layer and pressed down firmly to make a good contact; and (2) then Quickly pull off the tape, even if the surface of the layer is at an angle of 180 ° -54- 200408662

(48) The same is true. The sample is considered to pass if the layer remains intact on the wafer, or it is considered to fail if some or all of the film passes over the tape. Stud tensile test: Epoxy-coated studs are attached to the surface of a wafer containing the layer of the invention. A ceramic backplane is applied to the back of the wafer to prevent substrate bending and improper stress concentration on the stud edges. Then, the stud was pulled by the test device using a standard pulling force prescribed procedure in a direction perpendicular to the wafer surface. Then record the stress and interface position applied at the point of failure. Compatibility with solvents: Compatibility with solvents is determined by measuring film thickness, refractive index, FTIR spectrum and dielectric constant before and after solvent treatment. Regarding the compatible solvents, no significant change was observed. Example 1 Synthesis of 4,6-bis (adamantyl) resorcinolResorcinol (11.00 g, 100.0 mmol), bromogumurane (44.02 g, 205.1 mmol) and toluene (150 ml ) Add to a 250 ml 3-necked flask equipped with a nitrogen inlet, thermocouple and condenser. The mixture was heated to 110 ° C and became a clear solution. The reaction was allowed to continue for 48 hours, at which time TLC showed that all resorcinol had disappeared. The solvent was removed and the solid crystallized from hexane (150 ml). The disubstituted product was obtained in a white solid as a 66.8% yield (25.26 g). Another 5.10 g of product was obtained after silica gel column chromatography of concentrated mother liquor after the first harvest. The overall yield of the product was 80.3%. The product was characterized by proton NMR, HPLC, FTIR and MS.

-55- 200408662 (49) 4.6- For example, (adamantyl) resorcinol is polymerized into poly (extruded arsine) main chain bis (adamantyl) resorcinol (7.024 g, 18.57 mmol), FBZT (5.907 g, 18.57 mmol), potassium carbonate (5.203 g, 36.89 mmol), DM AC (50 ml) and toluene (25 ml) were added with a nitrogen inlet, a thermocouple, and Dean Stark ( Dean-Stark) collector in a 250 ml 3-necked flask. The reaction continued at this temperature for 1 hour and the temperature was raised to 165 ° C by removing some toluene. The aggregation process is monitored by GPC. When Mw = 22,000, the reaction was stopped. An additional 50 ml portion of DMAC was added to the reaction flask. The solid was filtered at room temperature and extracted with hot dichloromethane (2 x 150 mL). Methanol (150 mL) was added to the solution to precipitate a white solid, which was isolated by filtration. The yield was 65.8% (8.511 g). The solid was dissolved in tetrahydrofuran (150 ml) and methanol (300 ml) was slowly added to the solution. Shen Dian's white solid was passed; isolated and dried under vacuum at 90 ° C.

-56- 200408662 (50) Example IA: The composition was formed from the product of Example 1, a silane adhesion promoter, and a solvent, and was then spun on the substrate. Example 2-Synthesis of Alternative Polymers

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

Example 2 A57-200408662

The synthetic procedure described in Example 1 was followed except that 3,4-difluorotetraphenylcyclodienone was used as the difluoro compound. Example 2B: The composition is formed from the product of Example 2, a phenol-formaldehyde resin adhesion promoter, and a solvent, and then rotated on the substrate. Example 2C: The composition was formed from the product of Example 2A, a glycidyl ether adhesion promoter, and a solvent, and then was spun: on a substrate. Example 3 Anticipated Alternative Main Chain The following structures are expected typical main chains, which can be manufactured according to the general synthetic procedures of Examples 1 and 2. • 58 · 200408662 (52)

Example 3A: The composition was formed from the first polymer of Example 3, a non-planar, and a carboxylate adhesion promoter and a solvent, and was then spun on a substrate. Example 3B: The composition was formed from the second polymer, acetopyridine oligomer, or poly-59-200408662 (53) compound adhesion promoter and solvent of Example 3, and then was spun on the substrate. ——P and the compound is formed from the third polymer, ethylenene oligomer or polymer adhesion promoter and solvent of Example 3, and is then spun on the substrate. Example The composition was formed from the fourth polymer, ethylene heteroaromatic oligomer, or hydrate of Example 3 with a promoter and a solvent formed, and was then spun on a substrate. Example 4: The diamond-end-capped monomer shown in ^ Α 料 9B such as c.M.Lewis, L.J.

Mathias, N. Wiegai, ACS Polymer Preprints, 36 (2), 140 (1995) have been synthesized. Example 4A: I—. And σ is formed from the product of Example 4, an ethylene silane adhesion promoter, and a solvent are formed, and then is spun on the substrate. Example 5—This example illustrates the preparation of a thermosetting component (a). Synthesis of Tetrabromoadamantane fTBAl

The synthesis of 1,3,5,7-tetrabromoadamantane starts from commercially available adamantane and is based on e.g. GP Sollott and EE · Gilbert, j. Org · Chem ·, 45, 5405-5408 (1980), B. Schartel, V. Stumpflin, J. Wendling, JH Wendorff, W. -60- 200408662

(54)

Heitz, and R. Neuhaus, Colloid Polym. Sci., 274, 911-919 (1996), or AP Khardin, IA Novakov, and SS Radchenko, Zhi. Org. Chem., 9, 435 (1972) The synthesis procedure described above. Routine synthesis of up to 150 grams per batch. Step 2: 1,3 · 5 · 7-Di (3 / 4-bromobenzyl) adamantane (TBPA) and 1,3 / 4-bis "I η" / 4 " -Bromobenzyl) adamantyl 1 Synthesis of a mixture of stupid ΒΤΒΡΑΒ)

In the first step, TBA is reacted with bromobenzene to assume that 1,3,5,7-methyl (3 / 4-bromophenyl) adamantane (TBPA) can be obtained, such as Macromolecules, 27, 7015-7023 (1994 ) (Above). HPLC-MS analysis showed that the desired TBPA in all reaction products was present at about 50%, with 40% tetraphenyl apatine tiger bromide and about 10% tetraphenyl adamantane dibromide.

-40% to 0% To be clear, the experimental procedure of step 2 above is as follows:

Combined dry 5 liter 3-necked round bottom flask, condenser, magnetic stirrer, heating sleeve, thermocouple, thermal controller unit and N2 inlet-outlet for 30% KOH solution. The flask was purged with N2 for 10 minutes. 2 liters (62% v / v of total volume) was poured into the flask and the stirring rod was activated. Add D88 (160.00 ± 0.30 g) and the funnel is cleaned with 1 liter (31% v / v of total volume) bromobenzene. Remove the raw material HPLC • 61-200408662

The samples were compared with 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. The solution at this time was dark purple without visible precipitation. The reaction mixture was stirred at room temperature for 1 hour. After 1 hour, the temperature of the reaction mixture rose to 40 ° C. After the temperature reached 40 ° C, the reaction mixture was stirred for 3 hours. HPLC samples were taken at time 1 + 3.0 at 40 ° C. When no trace TBA was seen on the HPLC chromatogram, the reaction was complete. When the reaction is complete, the dark reaction mixture is poured into a 20-liter reactor containing 7 liters (217% v / v relative to the total bromobenzene volume), 2 liters (62% v relative to the total bromobenzene volume v) / v) ice and 300 ml (3 7%) HC1 (9% v / v relative to total bromobenzene volume). Use an overhead stirrer to vigorously stir the reaction mixture for 1 hour and 10 minutes. The β organic layer was transferred to the separation chamber and washed twice with 700 ml (22% v / v relative to the total bromobenzene volume) of deionized water. The washed organic layer was placed in a 4 liter separation funnel and 16 liters (5x times the volume of total bromobenzene) of methanol was added as a slow stream. The methanol was placed in a 30 liter reactor under a high-priced stirrer to settle within 25 minutes and 5 minutes solid. After the addition is complete, vigorously stir the methanol suspension for 1 hour ± 10 minutes. The methanol suspension was filtered by suction through a Buchner funnel (1 85 ml). The solid was washed on the filter cake with three 600 ml portions (19% v / v relative to the total bromobenzene volume) of methanol. The solid was sucked dry for 30 minutes. The resulting light red powder was emptied into a crystallizer tray using a trowel and placed in a vacuum oven to dry overnight, and then weighed after drying. The powder was dried for another 2 hours in a vacuum oven until the weight changed to < 1%, and then weighed again. After drying the solid, record the final weight and calculate the yield. The products are about 50% TAPA, 40% tetraphenyljinbo 1Jane tribromide and 10% tetraphenyl dibromide 200408662 (56) 1 ^^^ as mentioned above. The yield was 176.75 g. 30% by weight of 8 to 8 to 8 was formed. Step 3: Synthesis of TBPA and BTBPAB

Mixture of para, meta isomers of tetra, tri and dibromo derivatives

{rsvrnlrI ΒΓ US I a

1,3,5,7-Di (3 '/ 4, bromophenyl) adamantane (mixture of para and meta isomers) However, unexpectedly, when the previous product mixture was subjected to fresh reagents and catalysts (Bromobenzene and A1C13, 1 minute at 20 ° C), the TBPA ratio of the tetrabromide, tribromide and dibromide monomer mixture increased from about 50% to about 90-95%. 3-5 wt% BTBPAB is still present. This result was unexpectedly repeated by applicants -63-200408662

(57) confirmations and this resulted in a novel method of converting the previous mixture of thermosetting component (a), as described below and in Figure 11. Specifically, the experimental procedure of step 3 above is as follows. The equipment used is the same as in step 2 above. The corresponding amount of bromobenzene and aluminum bromide required was calculated based on the yield of TBPA synthesized by the above / traditional synthesis method. An appropriate amount (from 80% Wv by volume) of bromobenzene was poured into the flask and the stirring rod was activated. A sufficient amount of TBA synthesized from step 2 above was added and the funnel was washed with an appropriate amount (from the entire volume of 10% v / v) bromobenzene. A raw HPLC sample was taken and compared to a standard HPLC chromatogram. A sufficient amount of aluminum bromide was added to the solution and the funnel was washed with the remaining (10% of the total volume) bromobenzene. The solution at this time was dark purple without visible precipitation. The reaction mixture was stirred at room temperature * 17 minutes. After 5 minutes and 17 minutes, HPLC samples were taken. The reaction was complete when the spike group corresponding to TBPA was dominant in the HPLC chromatogram. When the reaction is complete, the dark reaction mixture is poured into a 20 liter reactor, which contains 7 liters (217% v / v relative to the total bromine volume) deionized water, 2 liters (62% v relative to the total bromine volume v / v) Ice and 300 ml (37%) HC1 (9% v / v relative to the total volume of bromobenzene), and stir vigorously with an overhead stirrer for 1 hour ± 10 minutes. The organic layer was transferred to a separation funnel and partially washed twice with 700 ml (22% v / v of total bromobenzene volume) deionized water and partially saturated with 700 ml (700% (22% v / v of bromobenzene volume) of saturated NaCl solution. Wash three times. After washing the organic layer, put it in a 4 liter separation funnel and add an appropriate amount (5x times the volume of total bromobenzene) of methanol as a slow flow. Place the 30 liter reactor under the high-priced stirrer to precipitate solids for 25 minutes ± 5 minutes . After the bonus is completed, strong 200408662

(58) Stir the ethanol suspension for 1 hour ± 10 minutes. The methanolic suspension was filtered by suction through a Buchner funnel (185 ml). The solid was washed with three portions of 600 ml (19% v / v relative to the total bromobenzene volume) methanol on the filter cake. Dry the solid for 30 minutes. The resulting light red powder was emptied into a crystallizer tray using a trowel and placed in a vacuum oven to dry overnight, and then weighed after drying. The powder was dried for another 2 hours in a vacuum oven until the weight changed to < 1%, and then weighed again. After drying the solid, record the final weight and calculate the yield. The yield was 85.5%. Step 4: 1,3,5,7-, "374 ·-(benzylethynyl) mosyl-1adamantane (TPEPA) and U3 / 4-bis, Γ, 3 ', 5, parabenzyl ethynyl) Synthesis of Benzoyl 1-Ganggang Pinane} Blend (BTPPEPAB) 200408662 (59)

The mixture of TBPA and ΒΓΓΒΡΑΒ is reacted with phenylacetylene to obtain the final product, which has 95-97% by weight of 1,3,5,7-^ [374 *-(phenylethynyl) phenyl] adamantane (TPEPA)- As a mixture of isomers-according to the general reaction of palladium-catalyzed Heck acetylation stipulated with 3-5% by weight 200408662

(60)-(phenylethynyl) phenyl] adamantyl} benzene (BTPEPAB) as a mixture of meta and para isomers was confirmed by GPC, NMR and HPLC. A mixture of TBPA and BTBEBAPA made by a reaction that includes TBPA is soluble in cyclohexane. Specifically, the experimental procedure of this step 5 synthesis method is as follows. Combine the following equipment: dry 2 liter 3-necked round bottom flask, water condenser, overhead stirrer, heating sleeve, thermocouple, thermal controller unit, dropping funnel, 2-neck adapter, and 30% 〇〇Η Solution N2 inlet-outlet. The flask was purged with osmium for 10 minutes. Weigh the mixture of TBPA and BTPBAB from the synthesis procedure in step 3 above. Triethylamine (TEA) (total calculated TEA volume minus 300 ml) was added to the reaction flask, the overhead stirrer was operated, and then the compound shown in the following sequence was added: dichlorobis (triphenylphosphine) palladium [II] Medium, wash the funnel with 50 ml (4% of the total volume) TEA and stir for 5 minutes; triphenylphosphine, wash the funnel with 50 ml (4% of the total volume) TEA and stir for 5 minutes; and copper (I) iodide Wash the funnel with 50 ml (4% of the total volume) TEA and stir for 5 minutes. Add the entire amount of TBPA synthesized from Step 3 above and shake 100 ml (8% of the total volume) of the TEA cleaning funnel. The flask was heated to 80 ° C. Once the temperature of the reaction mixture reached 80 ° C, a HPLC sample was taken for analysis. This is the raw material.

The resulting phenylacetylene diluted by 50 ml (4% of the total volume) of TEA was placed in a dropping funnel (the funnel was attached to one of the necks of a 2-neck adapter). The diluted phenylacetylene was added dropwise to the reaction mixture over 30 minutes ± 10 minutes. This is an exothermic reaction, and the temperature is controlled with a water bath. The exotherm lasted 3 hours. After heating at 80 ° C for 3 hours, the reaction was stopped. Sampling at 80 ° C for 3 hours HPLC 200408662

(61) The reaction mixture was cooled to 50 ° C and then filtered through a Buchner funnel (85 mm). The crude solid was washed twice with 600 ml of TEA (v / v% = 52% of the calculated TEA volume). The filter cake was placed in a 4-liter winding cup, and the contents were stirred with 1 liter of TEA (v / v% = 87% of the calculated TEA volume) at room temperature for 15 minutes. The filter cake was passed through a Buchner * funnel (185 mm) and the crude solid was washed with 300 ml TEA (v / v% = 26% relative to the calculated TEA volume). The solids were allowed to dry overnight. HPLC, DSC, trace metals and UV-VIS were performed on a 3 g sample of the crude product. The differences between the prior art and the present invention are explained below. Figures 11 and 12 show the preparation of the following isomers. The Roman numerals in this example correspond to the Roman numerals of Figures 11 and 12. As stated in the background paragraph 1, Reichert's goal is to define the structure's 1,3,5,7-[[4-phenylethynyl) phenyl] adamantane, that is, the single para isomer of this compound -1,3,5,7 · [4 ·-(phenylethynyl) phenyl] adamantane (VIII). This and this compound, which has only a well-defined structure that can be characterized by analytical methods, is the goal of Reichert's work.

Reichert's plan can achieve the following sequence: .- 1,3,5,7-tetrabromoadamantane (I) — 1,3,5,7- ((4, -bromobenzyl) jingang) jane (11 ) (Para-isomer) —1,3,5,7-[[4, (phenylethynyl) benzyl]] adamantane (VIII) (para-isomer)

Reichert's failure in steps (I)-(II) is that its tolerance is available, 3,5,7 · (374, -bromobenzyl) adamantane (III)-1,3,5,7- A mixture of isomers of (bromophenyl) adamantane contains a combination of para- and meta-bromophenyl groups attached to the adamantane core (see below), and it is considered that the work objective has not been achieved. To support it, it states: "The lack of regional selection during arylation keeps us from -68- 200408662

(62) Willing to further carry out Friedel-Crafts reaction on adamantane, which will lead to further research on the derivatization of easily formed 1,3,5,7-tetraphenyladamantane (VI) ". In order to prepare a single para-isomer, 丨, 3,5,7-[[4 ^ (phenylethynyl) phenyl]] adamantane (VIII), a "detour procedure" is designed as follows: 1, 3, 5,7-tetraphenyladamantane (乂 1) —1,3,5,7- 肆 (4, -iodophenyl) adamantane (VII) — 1,3,5,7- 肆 [4'- (Phenylethynyl) phenyl] adamantane (VIII) Reichert successfully achieved this sequence and isolated a single para-isomer (VIII), but the solubility of this compound became so low that 1 of this compound could not be obtained : > C NMR spectrum. Reichert observed that compound 3 [(VIII)] was found to be sufficiently soluble in chloroform to obtain a 4 NMR spectrum. However, it was found that the search time was not practical for obtaining nC NMR spectra. Solid state NMR was used to confirm the product. Reichert. Diss. (Ibid.) 9 To confirm this result, Reichert's compounds were tested with several standard organic solvents and found to be insoluble in virtually every organic solvent tested. In other words, Reichert prepared 1,3,5,7-di (3, / 4, -bromophenyl) adamantane (III), but did not continue in this direction because the product was not a single isoform with a well-defined structure Constituency. In turn, it prepares the 1,3,5,7-iso (4, iodophenyl) para-isomer of rimantad (VII) and converts it to 丨, 3,5,7-iso [4 '-(benzene The single isomer of the ethynyl) phenyl] adamantane (VIII) 'which becomes insoluble' cannot be used. Applicants and others repeated the reaction of 1,3,5,7-tetrabromoadamantane with bromobenzene if it was a thousand times and the analysis of the reaction of 1,3,5,7-tetrabromoadamantane with bromobenzene showed that it was not 1, 3,5,7-H (37 4'-bromophenyl) adamantine (111) (as proposed by Reichert) 'and 1,3,5,7-H (31/4, -bromophenyl) adamantane (III) Equivalent to approximately 1-phenyl 200 408 662

(63) -3 5 A mixture of 7-ginseng (3, / 4, -bromophenyl) adamantine (IV). This conclusion can be confirmed by LC-MS research and elemental analysis. The cause of the reaction process was found. Bromobenzene is known to be substantially free of the conditions of the Friedel-Crafts reaction.

Dear, J. Org. Chem., 27, 3441-3449 (1962)) · 2 P1ιΒγ- > P1ιΗ + Βγ2Φ As the solubility of benzene in the reaction mixture increases, it begins to replace [or bromine in (III)] The ratio of benzene is so high that the rapidly established equilibrium results in approximately equal amounts of (III) and (IV) °. Therefore, 1,3,5,7-di (3, / 4, -bromophenyl) adamantane cannot be obtained (111) (as proposed by Reichert); instead, it has 1,3,5,7-((374, -bromophenyl) adamantane (111) and 1-phenyl-3,5,7-ginseng (3 , / 4, bromophenyl) adamantane (to) about 1: 1 mixture. In order to shift the equilibrium towards the 1,3,5,7- (3, / 4, bromophenyl) adamantane (in) side, the fresh part of bromobenzene was used to treat 1,3,5,7 in the presence of a brominated chain -The solid reaction product of tetrabromoadamantane and bromobenzene (3, / 4, -bromophenyl) adamantane (III) and phenylphenyl-3,5,7-shen (3, / 4, bromophenyl) ) 1: 1 complex of adamantane (IV)]. As a result, pure bromobenzene was replaced directly by ^ -3,5,7-bromo (3, / 4, bromo-benzyl) Benzyl in King Kong Hyun (IV), so that the product to be resolved contained about ^ in 30 seconds. 90-9 5% 1,3 ,: >, 7-Di (3 '/ 4, bromobenzyl) adamantane (III) This situation is under a room shade, and observed for about 5-10 minutes', and then slowly increase benzene The concentration of 丨 -phenyl '-3,5,7-shen (374f-bromophenyl) adamantane (IV) increased, several hours • 70- 200408662 (64), using approximately the same concentration of 1, 3,5,7- (3 '/ 4f-bromophenyl) adamantane (III) and 1-phenyl-3,5,7-shen (3' / 4, bromophenyl) adamantane (IV) Re-establish the balance. Therefore, 1,3,5,7- (3 '/ 4, bromophenyl) adamantane (III) (reichert synthesis) can be borrowed in the presence of aluminum bromide 1,3,5, 7-tetrabromoadamantane and bromobenzene solid / reaction product prepared by the second treatment. 1,3,5,7- (3 · / 4'-bromophenyl) adamantane (III) and phenylacetylene The Heck reaction provides a 95-97 wt% 1,3,5,7-tetrakis [374, (phenylethynyl) phenyl] adamantane (V) (a mixture of para and meta isomers formed. Shape The five isomers include (1) para, para, para, para-; (2) para, para®, para, meta-; (3) para, para, meta (4) para, meta, meta, meta-; and (5) meta, simple, meta, meta-. Trace ortho isomers can also exist. ) With 30% by weight of 1,3 / 4-bis {Γ, 3 ', 5'-para [3 ”/ 4” -phenylethynyl] phenyl} adamantyl} benzene (14 isomers are formed .) A novel mixture which is confirmed by GPC, NMR and HPLC and is soluble in toluene, xylene, cyclohexanone, phenyl ether, propylene glycol methyl ether acetate, mesitylene, cyclohexyl acetate, etc. For example The solubility in cyclohexanone is> 20%. This characteristic makes it spin-coatable, which can ensure the practical use of this material, especially in the field of laminates and semiconductors. Therefore, the intermediate 1 prepared by the present invention , 3,5,7- (3 '/ 4, bromophenyl) adamantane (III) provides opportunities to make 1,3,5,7-tetrakis [3' / 4f- (phenylethynyl) phenyl] Adamantane (乂) and 1,3 / private bis {1 |, 3 |, 5, and [3 " / 4'phenylethynyl] phenyl} gold: adamantyl} . (Soluble mixture of para-isomer and Q), which may be used: as the thermosetting component (a) Example 6 -71--200408662

(65) This example illustrates the preparation of another thermosetting component (a). Step 1: Synthesis of meta- and para-bromodibenzylidene isomers

In a 500 ml 3-necked round bottom flask equipped with an addition funnel and a nitrogen inlet, 4-iodobromobenzene (25.01 g, 88.37 mmol), triethylamine (300 ml), and bis (tribenzene) were added. Phosphine) Palladium [II] chloride (0.82 g) and copper iodide [I] (0.54 g) Then slowly add a solution of phenylacetylene (9.025 g, 88.37 mmol) in triethylamine (50 ml) The temperature of the solution was kept stirred at 35 ° C. After the addition was complete, the mixture was stirred for another 4 hours. The solvent was evaporated on a rotary evaporator and 200 ml of water was added to the residue. The product was dichloromethane (2x150 ml) ) Extraction. Combined organic layers, solvent was removed by rotary evaporator. The residue was washed with 80 ml of hexane and filtered. HPLC showed pure product. (Yield, 19.5 g, 86%). Additional purification system. By short silica column Chromatography (eluent: a 1: 2 mixture of toluene and hexane). After the solvent was removed, a white crystalline solid was obtained. The purity of the product was characterized by GC / MS in an acetone solution, and further Characterized by proton NMR. Step 2: Synthesis of meta- and para-acetylene dibenzylacetylene (^ -〇ξ €- · Βγ ~ 〇 ~ c ^ c ^) ~ c " c The synthesis of para-acetylene diphenylacetylene from para-brominated diphenylacetylene is performed in two steps. In the first step, the para-brominated diphenylacetylene system Use of Trimethyl Methyl72-200408662

(66) Silylacetylene (TMSA, as shown above) is trimethylsilylacetylated, and in the second step, the reaction product of the first step (i) is converted to the final product. Step 骡 a (trimethylsilyl acetylation of 4-bromodiphenylacetylene): 4-bromodiphenylacetylene (10.285 g, 40.0 mmol), ethynyltrimethylsilane (5.894 g, 60 · 0 mmol), 0.505 g (0.73 mmol) dichlorobis (triphenylphosphine) palladium [II] catalyst, 40 ml of anhydrous triethylamine, 0.214 g (1.12 mmol) copper iodide [ I] and 0.378 grams (1.44 millimoles) of triphenylphosphine were placed in a 5-liter 4-necked round bottom flask equipped with an overhead mechanical stirrer, a condenser, and N2 removal positioned in a heating sleeve. The mixture was heated to a gentle reflux (about 88 ° C) and kept under reflux for 1.5 hours. The reaction mixture became a thick black paste and was cooled. TLC analysis showed that the starting material, 4-bromodiphenylacetylene, was completely converted into a single product. The solid was filtered and washed with 50 ml of triethylamine, mixed with 400 ml of water and stirred for 30 minutes. The solid was filtered and washed with 40 ml of methanol. The crude solid was recrystallized from 500 ml of methanol. When left to stand, bright silver crystals settle out. It was isolated by filtration and washed with 2 x 50 ml of methanol. Recoverable 4.662 g (42.5% yield). Step b (Conversion of 4- (trimethylsilyl) acetylene diphenylacetylene to 4-acetylene diphenylacetylene) · 800 ml of anhydrous methanol, 12.68 g (46.2 mmol) of 4- (trimethylsilyl) ) Acetylene diphenylacetylene and 1.12 grams of anhydrous potassium carbonate were charged into a 1-liter 3-necked round bottom flask equipped with a nitrogen inlet and an overhead mechanical stirrer. The mixture was heated to 50 ° C. Continue stirring until no starting material is detected by HPLC analysis (approximately 3 hours). The reaction mixture was cooled. The crude solid was stirred in 40 ml of dichloromethane for 30 minutes and filtered. The filtered suspended solids showed mainly impurities by HPLC. The dichloromethane filtrate was dried and evaporated to give 8.75 g of solid 200408662

(67) body. When the bath was further dried in the furnace, the final weight was 8.67 g, which represented a yield of 92.8%. Step 3: 1,3,5,7- 肆-丨 37 4 ·-"(4 ··-(benzylethynyl) benzylethynyl1benzyl} Kaneoka" j alkane (TPEPEPA) 1.3 / 4-bis {1 ', 3'.5, Synthesis of f 3π / 4 "-" 4π >-( Benylethynyl) benzylethynyl 1benzyl adamantyl! Benzyl (ΒΤΡΕΡΕΡΑΒ)

c = cu

-74-200408662 (68)

The mixture of TBPA and BTBPAB (above) is reacted with 4-acetylene diphenylacetic acid to obtain 1,3,5,7- 肆-{3 '/ 4f- [4 "-( Phenylethynyl) phenylethenyl] benzyl} adamantane-75-200408662 (69) (TPEPEPA) and 1,3 / 4-bis {l ,, 3f, 5, -see {3f, / 4, The final product of a mixture of '-[4π- (phenylethynyl) phenylethynyl] phenyl} adamantyl} benzene (BTPEPEPAB). Example 7 A thermosetting component (a) (200 g) prepared by a procedure similar to that of Example 5 above was charged into a flask. Cyclohexanone was added to the flask in an amount of 5.4 times the thermosetting component (a) and the flask was shaken. The adhesion promoter (b) used was polycarbosilane (CH2SiH2) q, where q was 20-30, 0.268 times the amount of the thermosetting component (a) was added to the flask and shaken. The final solution contains 15% by weight of thermosetting component (a) and 6.7% by weight of polycarbosilane adhesion promoter (b) based on the thermosetting component (&). Regarding reflux, a dry 1 liter 3-necked round bottom flask with a magnetic stirring rod, a condenser with an N2 inlet-outlet, an oil bath with a thermal controller and a thermocouple, and a thermocouple with an adapter were used. The solution boiled under reflux for about 23 hours. The reaction mixture was cooled to 120 ° C. Install the Dean-Stark collector and fill it with toluene. Toluene was added to the refluxing solution in an amount of 0.1 to 15 times the amount of the thermosetting component (a) (ml). Enhanced boiling and azeotroping started at 130 ° C and continued for about 40 minutes until water evolution ceased. The temperature of the reaction mixture increased to 148 ° C. Toluene and water were discharged from the collector and azeotropically continued until 0.1 65 times the amount of toluene and cyclohexanone as the thermosetting component (a) were added to the distillation. Flask temperature reached 1 53-1 55 ° C 'The reaction mixture was cooled to room temperature. Cyclohexanone was added to make the solution 15% by weight of the composition of the present invention comprising a thermosetting component (a) and a polycarbosilane component adhesion promoter (b). GPC showed oligomer formation. -76- 200408662

(70) The following examples relate to the layers forming the composition of the present invention and the layers of the conventional composition. Example 8 Comparative A is a polyarylene ether disclosed by Honeywell U.S. Patent 5,986,045. Regarding Example 8, the composition of Example 7 was applied to the substrate using the coating conditions of Table II: Table II Step Method Rotation (RPM) Time (seconds) 1 Assignment 0 2,8 2 Delay 0 1.7 3 Dispersion 1000 1 2 4 Spin 2000 40 5 BSR 1500 6 6 EBR 400 12 7 EBR 800 7 8 Dry 1000 7 9 Dry 1500 5 10 End 0 0.06

In Table II, BSR stands for rear side cleaning and EBR stands for edge cleaning. The applicator used was DNS SC-W80A-A VFDLP, the pressurized gas was helium, the distribution pressure was 0.08 MPa, the distribution rate was 1.0 ml / sec, and the in-line filter was 0.1 micron PFFV0D8S (Millipore, Fuluoroline- S). The obtained spinning composition was baked at a temperature of 150 ° C, 200 ° C, and 250 ° C under N2 (< 50 ppm 02) for 1 minute, respectively. The oven curing conditions are at N2R 40 (TC calendar -77- 200408662

60 minutes and rise to 250 ° C at 5 ° K per minute. The temperature range is 350 ° C to 450 ° C. Alternatively, hot plate curing conditions can be used at N2R 350 ° C to 450 ° C for 1-5 minutes. The obtained layer was analyzed according to the analysis test method described above. The properties of the layers are shown in Table III. Table III Properties Comparison A Example 8 Electrical properties: Dielectric constant (SaiviHx 2.85 2.65 Burst voltage (MV / cm) > 2 > 2 Thermal properties: Shrinkage (%) after 400 ° C / 10 hours 1.2 1.0 in Shrinkage (%) after 425 ° C / 10 hours 4.0 2.0 ITGA weight loss rate after 425 ° C / 0-30 minutes 1.2 0.5 ITGA weight loss rate after 425 ° C / 30-150 minutes 1.6 0.8 Mechanical: τ / c) First cycle 400 > 430 Tg (° C) Second cycle 400 > 450 modulus (GPa) 5.0 6.5 Hardness (GPa) 0.4 0.8 The tensile strength of the stud screw is in the form of ^) > 11 > 10 Tape test passes refractive index @ 633 nm 1.675 1.627 Compatible with solvents Yes

-78-200408662

(72) Visual inspection confirmed no streaks. The Tg improvement can obviously be used in difficult high-temperature processing environments, and the modulus improvement can promote product integration. Example 9-1 1 Comparative B is a 100% thermosetting component (a) and therefore does not contain an adhesion promoter (b). Regarding Examples 9-U, except changing the amount of polycarbosilane adhesion promoter, according to Example 8 to produce the composition of Table IV. The polycarbosilane component (b) used is (CH2SiH2) q, where q is 20-30.

Table IV Comparative B Example 9 Example 10 Example 11 Component 03) (% by weight) 0 3 6.7 10 Refractive index: 1.702 1.693 1.628 1.676 after curing 1.629 1.619 1.614 1.615 after curing Not after annealing at 425 ° C / 10 hours Measurement 1.612 1.607 1.606 Thickness: (A) After baking 8449 8134 8629 8452 After curing 9052 8711 9147 8898 Not measured after annealing at 425 ° C / 10 hours 8608 9019 8775 Thickness change (%): Baking versus curing 7.1 7.0 6.0 5.3 Cured versus annealed not determined -1.2 -1.4 -1.4 Note: Tape test, As-prep passed Passed the test after passing boiling water failed Passed the tensile strength of the stud 0 9.4 9.1 6.1 • 79- 200408662

Therefore, specific examples and applications of compositions and methods for producing low dielectric constant polymers have been disclosed. However, those skilled in the art will understand that, besides those already described, various modifications can be made without departing from the concept of the invention. Therefore, except for the spirit of the scope of the attached patent application, the main substance of the present invention is not limited. In addition, in clarifying the scope of the specification and patent application, all terms should be set forth in the broadest manner consistent with the context. In particular, the terms "comprising" and "including π" shall refer to steps that are elements, components, or non-absolute, indicating that the referenced element, component, or step may be presented or used,

Or in combination with other elements, components, or steps that are not clearly referenced.

-80-

Claims (1)

200408662 Patent application scope 1. A composition comprising: (a) a thermosetting component, wherein the thermosetting component comprises a monomer Ri having the following structure Dimer Ri R4 R3 Rs Or a mixture of the monomer and the dimer, wherein Y is selected from cage compounds and silicon atoms; Ri, R2, R3, R4, R5, and R6 are independently selected from aryl, branched aryl, and arylene ether; At least one of aryl, branched aryl, and arylene ether has ethynyl; 117 is aryl or substituted aryl; and at least one of Ri, R2, R3, R4, R5 and Rule 6 contains at least two iso Structure; and (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionality; may be the same or different, and the first functionality may interact with the thermosetting component (a) when the combination When an object is applied to the substrate, the second functionality may interact with the substrate. 2. The composition as claimed in claim 1, wherein the aryl group comprises a group selected from (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and 200408662. Part of a group consisting of (phenylethynyl) phenylphenyl. 3. The composition according to item 1 of the patent application scope, wherein the Y is selected from the group consisting of adamantane or adamantane. 4. The composition as claimed in claim 1, wherein the monomer is present. 5. The composition according to item 4 of the patent application, wherein the monomer is 1,3,5,7-[[3 '/ 4'-(phenylethynyl) phenyl] adamantane. 6. The composition of claim 1 in which the dimer is present. 7. The composition according to item 6 of the patent application, wherein the dimer is 1,3 / 4-bis {Γ, 3,5 ^ reference [3 ”/ 4”-(phenylethynyl) phenyl] Adamantyl} benzene. 8. The composition as claimed in claim 1 wherein a mixture of the monomer and the dimer is present. 9. The composition as claimed in claim 8 in which the monomer is 1,3,5,7-[[3 '/ 4 ^ (phenylethynyl) phenyl] adamantane and the dimer is 1,3 / 4-bis {1 ·, 3 ', 5 · -reference [3 &quot; / 4 ”-(phenylethynyl) phenyl] adamantyl ·} benzene. 10. As the first item in the scope of patent application Composition, wherein the at least two isomers are meta and para isomers. 11. The composition according to item 1 of the patent application range, wherein the adhesion promoter (b) is selected from the group consisting of Group: (i) Polycarbosilanes of formula (I): Η-Si—-Rg- R10-Si— Rn R12Si—Rj4- 〇—Rl3 Rl5Si —Rir I R16 abd 200408662 where Rs, R14 and R17 each independently represent Substituted or unsubstituted alkylene, cycloalkylene, acetylene, allyl, or aryl; R9, R10, Rn, R12, R15, and R16 each independently represent a hydrogen atom, alkyl, or alkylene Group, ethenyl, cycloalkyl, allyl, aryl, or arylene and may be straight or branched; R13 represents a silicone, silyl, siloxy, or organic group; and a, b, c And [4Sa + b + c + d <100,000] conditions with di, and b and c and d can be zero together or independently; (ii) Silane of formula (R18) f (R19) gSi (R20) h (R21) i, wherein R18, R19, R20 and R21 each independently represent hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted A substituted alkyl group, wherein the substituent is an amine group or an epoxy group, an unsaturated or saturated alkoxy group, an unsaturated or saturated polyacid group, or an aryl group; and at least two of R13, R19, R20, and R21 represent hydrogen, Hydroxyl, saturated or unsaturated alkoxy, unsaturated alkyl, or unsaturated carboxylic acid groups; and g + h + i &lt;4; (iii) a phenol-formaldehyde resin or oligomer of the formula -[Ι122 (: 6Η2 (〇Η) (Ι123)] γwherein R22 is a substituted or unsubstituted alkyl group, a cycloalkylene group, a vinyl group, an allyl group or an aryl group; R23 is an alkyl group, an alkylene group , Vinylidene, cycloalkylene, alkenyl or aryl; and j = 3-100; (iv) a glycidyl chain; (v) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group; and (vi) Ethylene cyclic oligomer or polymer, wherein the cyclic group is ethylene, aromatic or heteroaromatic. 12. The composition according to item 11 of the patent application scope, wherein the adhesion promotion Agent (b) 200408662 is the polycarbosilane. 13. An oligomer containing the composition as claimed in item 1 of the scope of the patent application. 14. A spinning comprising the composition as claimed in item 13 of the scope of the patent application and a solvent Composition. 15. The spinning composition according to item 14 of the patent application, wherein the solvent is cyclohexyl. 16.-a polymer made of an oligomer as item 13 of the patent application. 17. -A layer containing a polymer as claimed in item 16 of the scope of patent application 18. 18. a layer as claimed in item 17 of the scope of patent application, wherein the layer has a dielectric constant of Below 3.0. 19. A substrate having at least one of the layers as claimed in item 17 of the patent scope. 20.-A substrate having at least two of the layers as claimed in item 17 of the patent scope. 21. An electrical device comprising a substrate such as the scope of patent application No. 19. 22. A method for improving adhesion to a substrate, comprising the steps of: applying a composition layer to the substrate, the composition layer comprising: (a) a thermosetting component, wherein the thermosetting component comprises a structure having the following structure Monomer Ri 200408662 Dimer Ri r4 Rz R3 ..... R5 R6 or a mixture of monomers and dimers having the following structures, wherein γ is selected from cage compounds and silicon atoms; h, R2, R ;, R4, 115 and R6 are independently selected from aryl, branched aryl and arylene ether; at least one of aryl, branched aryl and arylene ether has ethynyl; R7 is aryl or substituted aryl; and, r2 , At least one of R3, R4, R5 and R6 contains at least two isomers; and (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, and the first functionality may be Interact with the thermosetting component (a) and the second functionality may interact with the substrate. 23. The method of claim 22, wherein the aryl group comprises a group selected from (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and (phenylethynyl) phenylbenzene Part of a group of foundations. 24. The method of claim 22, wherein the Y is selected from the group consisting of adamantane or gold steel. 25. The method of claim 22, wherein the monomer is present. 26. The method as claimed in claim 25, wherein the monomer is 1,3,5,7-methyl [3 74 '-(phenylethynyl) phenyl] adamantane. 27. The method of claim 22, wherein the dimer is present. 28. The method of claim 27, wherein the dimer is 1,3 / 4- 200408662 Bi {Γ, 3 ', 5'-reference [3 ”/ 4 &quot;-( phenylethynyl) phenyl] adamantyl} benzene β 29. The method according to item 22 of the patent application, wherein the monomer and A mixture of the dimers exists. 30. The method of claim 29, wherein the monomer is 1,3,5,7 · [3 '/ 4'-(phenylethynyl) phenyl] Adamantane and the dimer is 1,3 / 4-bis {Γ, 3,5'-reference [3 '· / 4π- (phenylethynyl) phenyl] adamantyl} benzene. 31. If applied The method according to item 22 of the patent, wherein the at least two isomers are meta and para isomers. 32. The method according to item 22 of the patent application, wherein the adhesion promoter (b) is selected from the following Compositions: (i) Polycarbosilanes of formula (I): Η I Si- R9 Rs ^ 10 -Si- Rn I12 • Si-R14 · 〇-r13 ab R15 Si —R17-- I R16 -d Among them, Rs, Rl4 and R17 each independently represent substituted or unsubstituted alkylene, cycloalkylene, ethylene, propyl or aryl; R9, R10, Rll, Rl2, Rl5 and ruler 16 each independently represents a hydrogen atom, an alkyl group, an alkylene group, an ethylene group, a cycloalkylene group, an allyl group, an aryl group, or an alkylene group and may be a straight chain or a branched chain; R13 represents an organic compound Group, alkoxy group or organic group; and a, b, c and d meet the conditions of [4Sa + b + c + dU00,000], and b and c and d may be zero together or independently; -6- 200408662 (The formula (18) "(1 ^ 9) 31 (1120)" 1121) 丨, in which 1 ^ 8, 1 ^ 9, feet 20, and R21 each independently represent hydrogen, a hydroxyl group, an unsaturated or saturated alkyl group, A substituted or unsubstituted alkyl group, wherein the substituent is an amine group or an epoxy group, an unsaturated or saturated alkoxy group, an unsaturated or saturated polyacid group, or an aryl group; and the R18, Ri9, R20, and R21 At least two of them represent hydrogen, a hydroxyl group, a saturated or unsaturated alkoxy group, an unsaturated alkyl group or an unsaturated carboxylic acid group; and f + g + h + i &lt;4; (iii) a phenol-formaldehyde resin or oligomer of the formula -[R22C6H2 (〇H) (R23)] j-where R22 is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl or aryl; R23 is alkyl, alkylene, Vinylene, cycloalkylene, allylic or aryl; and j = 3-100; (iv) a water glycerol chain, (v) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group; and ( vi) ethynyl cyclic oligomer or polymer, wherein the cyclic group is pyridox, aromatic, or heteroaromatic. 33. The composition according to item 32 of the patent application, wherein the adhesion promoter (b ) Is the polycarbosilane. 3 4. A composition comprising: (a) a thermosetting monomer 200408662 having the following structure wherein Ar is an aryl group; R, R, Rf3, R'4, Rf5 and Rf6 are independently selected from aryl, branch Chain aryl and arylene ether, and unsubstituted; and aryl, branched aryl and arylene ether each have at least one ethynyl group; and (b) an adhesion promoter comprising a compound having at least difunctionality, wherein The bifunctionality can be the same or different. The first functionality can interact with the thermosetting component (a) and when the composition is applied to a substrate, the second functionality can interact with the substrate. The composition according to item 34, wherein the adhesion promoter (b) is selected from the group consisting of: (i) a polycarbosilane of formula (I): Η ISi- R9 Rg * Rio-Si— R11 r12 • Si—R24— o—r13 Rl5 Si—R17 ab R16—d where Rs, 1 ^ 4 and each independently represent substituted or unsubstituted alkylene, cycloalkylene, ethylidene, or allyl or Rarylene; R9, R10, Rn, Rl2, Rl5 and R16 each independently represent a hydrogen atom, alkyl, alkylene, ethylene alkenyl, cycloalkyl, Propyl, aryl or arylene and may be straight or branched; Rn represents organosilicon, silyl, siloxy or organic; and a, b, c and d conform to [4 &lt; a + b + c +1 00,000], and b and c and d may be zero together or independently; (ii) a silane of formula (R18) f (R19) sSi (R20) h (R21) i, where R18, R19, R20 200408662 And r21 each independently represent hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl, wherein the substituent is amine or epoxy, unsaturated or saturated tigeroxy, unsaturated or saturated polyacid Or aryl; and at least two of R1S, R19, R20, and R21 represent hydrogen, hydroxyl, saturated or unsaturated alkoxy, unsaturated alkyl, or unsaturated carboxylic acid group; and f + g + h + i &lt;4; (iii) phenol-formaldehyde tree or oligomer of the formula-[R22C6H2 (〇H) (R23)] r where R22 is a substituted or unsubstituted alkynyl group, cycloendenyl group, ethoxylate Alkyl, alkyl, or aryl; Chin 23 is alkyl, alkylene, ethylidene, cycloalkylene, alkylene, or aryl; and j = 3-100; (iv) glycidic acid (V) an ester of an unsaturated carboxylic acid containing at least one carboxylic acid group; and (vi) a vinyl cyclic oligomer or polymer, wherein the cyclic group is pyridoxine, aromatic, or heteroaromatic. 36. The composition of claim 35, wherein the adhesion promoter (b) includes the polycarbosilane. 37. A spinning composition comprising a composition as described in claim 34 and a solvent. 38. A spin-drying composition as claimed in item 37 of the patent application, wherein the solvent is cyclohexanone β 39. A layer comprising a spin-show composition as claimed in item 37 of the patent application. 40. A method for manufacturing a low dielectric constant polymer precursor, including the following steps: 200408662 (l) Provide a composition comprising: (a) a thermosetting component, wherein the thermosetting component comprises a monomer Ri having the following structure Dimer r4 Ri Ri R3 χγί / ίΐιΐί R5 R6 Or a mixture of the monomer and the dimer, wherein γ is selected from cage compounds and silicon atoms; Ri, R2, R3, R4, R5 and independently selected from aryl, branched aryl, and arylene ether; aryl At least one of the group, branched aryl group and arylene ether has an ethynyl group; 7 is an aryl group or a substituted aryl group; and at least one of R2, R3, R4, R5 and R6 contains at least two isomers ; And (b) an adhesion promoting agent, comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, and the first functionality may interact with the thermosetting component (a) when the composition is coated When applied to the substrate, the second functionality can interact with the substrate; and • 10- 200408662 (2) The composition is treated at a temperature of about 30 ° C to about 350 ° C for about 0.5 to about 60 hours to form the 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-methyl [374, (phenylethynyl) phenyl] adamantane. 43. The method of claim 40, wherein the dimer is present. 44. The method according to item 43 of the scope of patent application, wherein the dimer is 1,3 / 4-bis {Γ, 3 ', 5, ref [3 ”/ 4” _ (phenylethynyl) phenyl] Adamantyl} benzene. 45. The method as claimed in the scope of patent application No. 40, wherein the mixture of the monomer and the dimer is present in β. 46. The composition, as claimed in the scope of patent application No. 45, wherein the monomer is 1, 3, 5, 7 -[3 '/ 4'-(phenylethynyl) phenyl] adamantane and the dimer is 1,3 / 4-bis {1 ', 3 \ 5 ·-ref [3' '/ 4 &quot; -(Phenylethynyl) phenyl] adamantyl} benzene. 47. The method of claim 40, wherein the adhesion promoter (b) is selected from the group consisting of: (i) Polycarbosilanes of formula (I): ΗI Si—R8 R9 ^ 10-Si— R 11 b R12 • Si—Rj4 * 〇—R〇R1S Si—RirI R16 d where Rs, R14 and R17 are each independently represented Substituted or unsubstituted alkylene, cycloalkylene, vinylidene, allyl, or aryl; R9, Rio, Rn, Ru, Rn, and Ri6 each independently represent a hydrogen atom, alkyl, or alkylene. -π-200408662 Alkyl, vinyl, cycloalkyl, allyl, aryl, or arylene and may be straight or branched; R i 3 represents organic crushed, crushed, oxy, or organic; and a, b, c and d meet [4 &lt; a + b + c + d &lt; 100,000] conditions' and b, c and d may be zero together or independently; (ii) Silane of formula (R18) f (R19) gSi (R20) h (R21) i, wherein R18, R19, R20 and R21 each independently represent hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted Substituted alkyl, wherein the substituent is amine or epoxy, unsaturated or saturated alkoxy, unsaturated or saturated carboxylic acid, or aryl; and at least two of R18, R19, R20, and R21 represent hydrogen , Hydroxyl, saturated or unsaturated alkoxy, unsaturated alkyl, or unsaturated carboxylic acid groups; and f + g + h + i &lt;4; (iii) a phenol-formaldehyde resin or oligomer of the formula -[R22C6H2 (〇H) (R23)] j-where R22 is a substituted or unsubstituted alkynyl group, a cycloalkylene group, an ethylene group, an amidino group or an arylene group; R23 is an alkyl group or an alkylene group Phenylene, ethylidene, cycloalkylene, allylic or aryl; and j = 100; (iv) glycidyl bonds; (v) esters of unsaturated carboxylic acids containing at least one carboxylic acid group; and (vi) a vinyl cyclic oligomer or polymer, wherein the cyclic group is pyridine, aromatic or heteroaromatic 3 48.-a method for manufacturing a low dielectric constant polymer, comprising the following steps: ( 1) Provide an oligomer comprising (a) a thermosetting component, wherein the thermosetting component comprises a monomer having the following structure-12-200408662 Ri Dimer Ri R4 r2 ^ / Ϋ ^ ΜΙιι, ... R3 R7 R6 R5 Or a mixture of the monomer and the dimer, wherein Y is selected from cage compounds and silicon atoms; Ri, R2, R3, R4, 115 and 116 are independently selected from the group consisting of aryl, branched aryl, and mystery; At least one of aryl, branched aryl, and arylene has ethynyl; R7 is aryl or substituted aryl; and at least one of Ri, R2, R3, R4, 115, and R6 contains at least two isomers And (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, and the first functionality may interact with the thermosetting component (a) when the composition is applied When reaching the substrate, the second functionality can interact with the substrate; and (2) polymerizing the oligomer to form the low dielectric constant polymer, wherein the polymerization includes a chemical reaction of the acetylene group. 49. The method of claim 48, wherein the Y is selected from the group consisting of adamantane and adamantane. 50. The method of claim 48, wherein the aryl group comprises a group selected from -13.200408662 Part of a group consisting of (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and (phenylethynyl) phenylphenyl. 51. The method of claim 48, wherein at least three of the aryl group, the branched chain aryl group, and the diaryl ether have an ethynyl group, and wherein the polymerization includes a chemical reaction of at least two of the ethynyl group. 52. The method of claim 48, in which all aryl, branched-chain aryl, and arylene ethers have ethynyl groups, and wherein the polymerization reaction includes a chemical reaction of ethyl groups. 53. The method of claim 48, wherein the monomer is present. 54. The method of claim 53 in the scope of patent application, wherein the monomer is 1,3,5,7-methyl [374 ·-(phenyl! Ethynyl) phenyl] adamantane. 55. The method of claim 48, wherein the dimer is present. 56. The method according to item 55 of the patent application, wherein the dimer is 1,3 / 4-bis {Γ, 3,5 · -reference [3 ”4”-(phenylethynyl) phenyl] adamantine Alkyl.} Benzene. 57. The method of claim 48, wherein a mixture of the monomer and the dimer is present. 58. The method of claim 57 in the scope of patent application, wherein the monomer is 1,3,5,7-z [374, (phenylethynyl) phenyl] adamantane and the dimer is 1,3 / 4-bis {1 ', 3', 5'-reference [3 "/ 4"-(phenylethynyl) phenyl] adamantyl} benzene. 59. The method of claim 48, wherein the at least two isomers are meta and para isomers. 60. The method of claim 48, wherein the thermosetting component (a) is dissolved in a solvent. 61. The method of claim 48, wherein the adhesion promoter (b) 200408662 Is selected from the group consisting of: (i) polycarbosilanes of formula (I): Η I-Si—r8 R9 R10-Si— R11 R12 • Si—R14- 〇-R13 Rl5_S | i-Rl7 'Rl6 abd Among them, R 8, R14 and R 17 each independently represent a substituted or unsubstituted alkylene, cycloalkylene, ethenyl, allyl or aryl; R9, Rio, Rn, R12, Rh and R16 each independently represents a hydrogen atom, an alkyl group, an alkylene group, an ethylenyl group, a cycloalkyl group, an allyl group, an aryl group or an arylene group and may be a straight chain or a branched chain; R13 represents an organic silicon, a silyl group, a silicon Oxy or organic groups; and a, b, c and d meet the conditions of [4Sa + b + c + dSl00,000], and b and c and d may be zero together or independently; (ii) A (R18) f (Rl9) gSi (R2〇) h (R2i) i crushed and burned 'where Ris, Ri9, R20, and R 21 each represent the hydrogen, the base, the endless and or saturated base, substituted or unsubstituted Alkyl, in which the substituent is amine or epoxy, unsaturated or saturated alkoxy, unsaturated or saturated carboxylic acid, or aryl; Han Yuan R 〖8 'Rl9' R20 and R21 Substituted nitrogen, light-based, absolute or unsaturated 'appearance oxygen, unsaturated alkyl or Unsaturated carboxylic acid group; and f + g + h + i &lt;4; (Hi) a phenol-formaldehyde resin or oligomer of the formula-[Κ22〇6Η2 (〇Η) (Ι123)] "--wherein R22 is substituted Or without replacement Base, cycloalkylene, vinyl, propyl, or aryl; r23 is alkyl, alkylene, vinylidene, cycloalkylene, allyl, or aryl; and j = 3-100; (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, wherein the cyclic group is pyridine, aromatic Or heteroaromatic. 62. A spinning low dielectric constant material, comprising: (a) a first main chain having a first aromatic moiety and a first reactive group and a first main chain having a second aromatic moiety and a second reactive group A second main chain, wherein the first and second main chains are crosslinked by the first and 1 second reactive groups in a crosslinking reaction, and the cage structure is covalently bonded to the first and second At least one of the main chains, in which the cage structure contains at least 8 atoms; and (b) an adhesion promoter comprising a compound having at least difunctionality, wherein the difunctionalities may be the same or different, and the first functionality may be the same as The first and second main chains interact and when the material is applied to the substrate, the second functionality can interact with the substrate. 63. The spin-on low dielectric constant material as claimed in item 62 of the patent application, wherein the aromatic portion includes a phenyl group. 64. The spin-on low-dielectric constant material according to item 62 of the application, wherein at least one of the first reactive group or the second reactive group contains an ethynyl group. 65. For example, the spin-on low dielectric constant material in the scope of patent application No. 62, in which the cage is 200408662 The structure includes at least one of diamond-fired and gold-steel cymbals. 66. The spin-on low-k material as claimed in item 62 of the patent application, wherein the cage structure includes substituents. 67. The spin-on low dielectric constant material according to item 62 of the application, wherein the adhesion promoter (b) is selected from the group consisting of: (i) a polycarbosilane of formula (I): Η I Si- R9 r8- R10 -Si— Rn r12 • Si—R14- 0—Rl3 a lb c Rl5 'Si — ^ 17-- r16 -d Rs, · R14 and Rl7 each independently represent substituted or unsubstituted alkylene, cycloalkylene, vinylene, allyl or aryl; R9, Rio, Rh, Ru, R15 and R16 each Independently represents a hydrogen atom, an alkyl group, an alkylene group, a vinyl group, a cycloalkyl group, an allyl group, an aryl group or an arylene group and may be a straight chain or a branched chain; 1113 represents an organic group, a crushed group, &gt; Oxo or organic group; and a, b, c and (1 meet the conditions of [4 幺 a + b + c + dS 100,000], and b and c and d may be zero together or independently; and R21 each independently &gt; Represents hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl, wherein the substituent is amine or epoxy, unsaturated or absolute alkoxy, unsaturated or saturated acid group Or aryl; and R [8, R19'R20 and at least two of them represent hydrogen, meridian, co and -17-200408662 Or unsaturated alkoxy, unsaturated alkyl, or unsaturated carboxylic acid groups; and f-τ-gh hr i &lt;4; (iii) a phenol-formaldehyde resin or oligomer of the formula-[R22C6H2 (OH) ( R23)] r wherein R22 is substituted or unsubstituted alkylene, cycloalkylene, vinyl, propyl or aryl; R23 is alkyl, alkylene, vinylene, cycloalkylene, Allylic or aryl; and j = 3-100; (iv) glycidol puzzle; (v) esters of unsaturated carboxylic acids containing at least one carboxylic acid group; and (vi) vinyl cyclic oligomers or polymers, wherein the cyclic group is pyridine, aromatic Or heteroaromatic. 68. —Spinned low dielectric constant polymer, including (a) a polymer having a hanging cage structure— [〇R24 (R25) m〇R26] n- , Where R24 is -C6H3-; R25 is adamantane, adamantane, (&lt;: ΰΗ5) ρ (adamantine) or (C (3H5) p (gold steel · appearance); m = 1-3; 11 = 1-10): ρ = 0 or 1; and rule 26 is a group of 2,3,4,5- (tetraphenyl) cyclodienone-1 or (b) an adhesion promoter, comprising A bifunctional compound, where the bifunctionality may be the same or different, the first functionality may interact with the polymer and when the polymer is applied to the substrate, the second functionality may interact with the substrate ^ -18-