JP3061194B2 - Electronic article comprising a fluorinated poly (arylene ether) dielectric - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to electronic articles comprising a fluorinated poly (arylene ether) dielectric.

Polymer films and coatings are often used as insulating materials and passivation layers in the electronics industry.
Particularly, it is used in an integrated circuit device such as a multichip module. Polymers with a low dielectric constant ε are preferred because the insulated elements can be designed for high circuit density, operate at high speed, and with little signal broadening. The effect of ε on multilayer integrated circuit articles is described in the Microelectronics Packaging Handbook.
ng Handbook), edited by Tummala et al., 687-692
Page, van Nost Reinhold
rand Reinhold; Watari et al., U.S. Patent No. 4,744,007 (1988); and Budde.
No. 4,732,843 (1988).

Polyimide is an insulator used in many electronic applications because of its excellent mechanical and thermal properties, and its suitability for processing thin films and coatings. However, polyimide has a relatively high ε, which is a limitation exhibited by the polyimide's tendency to absorb moisture in humid environments (up to 3-4%). Ε rises due to water absorption, and the performance decreases. One commercially available polyimide has an ε of about 3.2 at 0% relative humidity (% RH), which is about 3.8 at 60% RH.
To rise. Denton et al., "J. Electronic Mater." 14
As shown in (2), 119 (1985), moisture absorption of polyimide adversely affects performance due to an increase in the conductivity of the insulator, loss of adhesion, or corrosion. In addition, some polyimides are susceptible to hydrolysis and / or solvent attack (indicated by cracks or cracks that occur upon exposure to the solvent).

Mercer, United States Patent No. 4,835,19
No. 7 (1989) proposes to improve the solvent resistance of polyimide by curing with an acetylene, maleimide, or vinyl-terminated curing agent.
However, such cured polyimides have a significantly higher dielectric constant and a tendency to absorb moisture.

The present inventors have proposed using a fluorinated polymer having a binaphthyl group as the derivative material.

Polyquinoxaline, polyquinozalone, polybenzoxazole, and copolymers thereof with polyimides have also been described by Labadie et al., "SAMPE J.
J.) ", Vol. 25, pp. 18-22 (1989, November / December) as a polymer for microelectronics.

Kellman et al., "AS Simp
Siri (ACS Symp. Ser.) 326, "Phase Transfer Catalysis", 12
Page 8 (1987) discloses a method for preparing polyethers from diphenols and hexafluorobenzene and decafluorobiphenyl, but does not disclose the utility of the polymers thus prepared.
The same is true of Kellman et al., "Polym. Prepr., 22 (2), 383 (1981) and Gerbi et al.," J-Polym Poli Letters Ed. (J.Polym.Sci.Polym.Letters E
d.) ", 23,551 (1985).

The present invention provides an electronic article comprising a fluorinated poly (arylene ether) derivative material. This derivative material has a low dielectric constant, which is largely unaffected by increasing ambient humidity, can be made solvent resistant, and has good adhesion to itself and other adherends. Show.

SUMMARY OF THE INVENTION The present invention provides a compound of the formula: [Wherein -W- is [However, each -A is independently -F, -Cl, -Br, -C
_{F 3, -CH 3, -CH 2} CH = CH 2 or -C ₆ H _5; p is 0, 1 or 2; Z is a direct _{bond, -C (CH 3) 2 -} , - C (CF 3)
_{2 -, - O -, -} S -, - SO 2 -, - CO -, - P (C
_{6 H 5) -, - C} (CH 3) (C 6 H 5) -, - C (C 6 H 5) 2 -,
- (CF ₂₎ 1~6 _-, or (Here, -Y- is -O- or a direct bond) and m is 0, 1 or 2]; each -X is independently _{-H, -Cl, -Br, -CF 3} , - CH ₃ , −
CH ₂ CH = CH ₂ or -C ₆ H _5; q is 0, 1 or 2; comprising fluorinated poly (arylene ether) having n repeating units of the structure represented by 1 or 2] dielectric An electronic article comprising a body material is provided.

Preferably, -W- is And (Wherein -A, p, -Z-, m, -X, q and n are as defined above), corresponding to a fluorinated poly (arylene ether). Further, the -Z- group is preferably attached para to each etheric oxygen of the benzene ring.

In one aspect, an electronic article is a multi-chip module comprising a substrate, a plurality of semiconductor chips on the substrate and a multilayer interconnect connecting the semiconductor chips, wherein the multilayer interconnect comprises a plurality of conductive materials. And a plurality of dielectric material layers made of said fluorinated poly (arylene ether).

In another aspect, an electronic article has an integrated circuit chip having thereon a multilayer interconnect comprising a plurality of conductive material layers and a plurality of dielectric material layers made of the fluorinated poly (arylene ether). It is.

In yet another aspect, the electronic article is an integrated circuit chip having thereon a protective layer comprising the fluorinated poly (arylene ether). In yet another embodiment, the electronic article is a circuit board wherein the substrate is a fluorinated poly (arylene ether).

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1a shows a multi-chip module having a multilayer interconnect where the interlayer dielectric is a fluorinated poly (arylene ether) of the present invention. FIG. 1b shows a cross-sectional view of the multilayer interconnect.

FIG. 2 shows a cross-sectional view of an integrated circuit chip having a multilayer interconnect where the interlayer dielectric is the fluorinated poly (arylene ether) of the present invention.

FIG. 3 shows a cross-sectional view of an integrated circuit chip protected with a fluorinated poly (arylene ether) coating of the present invention.

FIG. 3a shows a cross-sectional view of a circuit board whose substrate is made of fluorinated poly (arylene ether).

FIG. 4 compares the dielectric constant of the polymer of the present invention with that of a control polymer not according to the present invention.

FIG. 5 shows a substrate having a plurality of multilayer devices having the crosslinked fluorinated poly (arylene ether) of the present invention as an interlayer dielectric.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The fluorinated poly (arylene ether) of the present invention can be prepared by condensation polymerization of diphenol (I) and fluorinated monomer (II): In the above formula, -W-, -X, q and n have the same meaning as defined above. Suitable diphenols (I) include
4 '-(hexafluoroisopropylidene) diphenol, 4,4'-(isopropylidene) -di (2,6-dimethylphenol), 4,4 '-(1-phenylethylidene) bisphenol, 4,4'- Isopropylidene diphenol, 9,9′-bis (4-hydroxyphenyl) fluorene, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, resorcinol and 4,6-dichlororesorcinol; Corresponds to a fluorinated poly (arylene ether) repeating unit.

Preferred diphenols (I) include 4,4 '-(hexafluoroisopropylidene) diphenol and 9,9'
-Bis (4-hydroxyphenyl) fluorene, and
1,5-dihydroxynaphthalene is mentioned.

Suitable fluorinated monomers (II) include hexafluorobenzene, decafluorobiphenyl, pentafluorobenzene, octafluorotoluene, 1,4-dibromotetrafluorobenzene, chloropentafluorobenzene, allylpentafluorobenzene, and 2,2 ′, 3,
3 ', 5,5', 6,6'-octafluorobiphenyl, Corresponds to a fluorinated poly (arylene ether) repeating unit. Preferred fluorinated monomers include hexafluorobenzene and decafluorobiphenyl.

Contrary to the customary in the art, complete fluorination of the aromatic ring in the monomer (II) is not necessary for a sufficient polymerization, but rather requires pentafluorobenzene, octafluorotoluene, 1,4-
Monomers such as dibromotetrafluorobenzene and chloropentafluorobenzene have been found to be suitable.

If a high molecular weight polymer is desired, two monomers are used in substantially stoichiometric amounts. Alternatively, if a low molecular weight material is desired, adjust the molecular weight with a slight excess of stoichiometric excess of either monomer, for example, to facilitate preparation of the solution for spin or other solvent coating operations. Can be.

An alkali metal carbonate, bicarbonate, or hydroxide is added to the polymerization mixture to convert the phenoxy group to the corresponding phenoxide. Sodium or potassium carbonate is preferred. A polar aprotic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, or 1-methyl-2-pyrrolidinone is used. The use of such solvents,
This is an advantage over other solvents such as nitrobenzene, which are more harmful and do not dissolve in water and require that the polymerization mixture be worked up in an organic solvent rather than water. The reaction is carried out at an elevated temperature, which must not be too high. About 50 ° C ~
Temperatures of about 125 ° C are usually suitable, with temperatures of about 60 to about 90 ° C being particularly preferred. Reaction times are typically from about 10 to about 72 hours.

The following repeating units are preferred: The polymer may be a homopolymer consisting essentially of a single repeating unit, such as one of the foregoing. Alternatively, a copolymer composed of a combination of the repeating unit of the present invention and another repeating unit of the present invention or a different type of repeating unit may be used. Fluorinated poly (arylene ether) copolymers can be prepared, for example, using two different diphenols (I) as comonomers or two different fluorinated monomers (II) as comonomers. Preferred copolymers have repeating units (A) and (N): Other preferred copolymers have repeating units (A) and (D). Yet another preferred copolymer has repeating units (A) and (O): Still other preferred copolymers have repeating units (A) and either repeating units (P) or (Q) or repeating units (D) and (Q): In copolymers wherein repeat units of the present invention are combined with repeat units of other types of polymers, at least 60 mole%, more preferably at least 80 mole% of the repeat units are fluorinated aromatic ether repeat units of the present invention. Is preferred. The copolymer may be an alternating, random, or block copolymer.

FIG. 1a shows a multichip module 1 according to the invention. Substrate 2 is typically made of silicon, glass or ceramic and supports a high density multilayer interconnect 3 in which the dielectric material providing insulation between the various layers is fluorinated poly (arylene ether). On the interconnect 3 are arranged semiconductor chips 4a to 4d, which are connected to one another by conductors in the interconnect 3. Substrate 1 may also include, for example, power and ground conductors. The lead frame 5 (numbered only one for simplicity) provides connection to external circuitry.

FIG. 1b shows a multilayer interconnect 3 supported on a substrate 2.
2 shows a partial sectional view of FIG. The electrical connection layers 10a-c are separated from one another by a fluorinated poly (arylene ether) dielectric 12. Vias 11 provide connections between the various layers as needed. Interconnect 3 is connected to an integrated circuit chip (not shown) by bond pads 13. The vias 11 are shown in this figure as stacked pillars, but other types common in the art, such as stepped or nested, may be used. Other designs of multi-chip modules in which the fluorinated poly (arylene ether) of the present invention is used as an interlayer dielectric include Blade,
"Overview of Multichip Technology", Electronic Materials Handbook (Electronic Mat)
erials Handbook), vol.1, Packaging ASM International
l), pages 297-312 (1989).

Fluorinated poly (arylene ether) can also be used as an interlayer dielectric during interconnection in combination with a single integrated circuit chip. FIG. 2 is a sectional view of this embodiment. The integrated circuit chip 15 has a plurality of fluorinated poly (arylene ether) dielectric layers 16 and a plurality of metal conductor layers 17 on its surface.

The fluorinated poly (arylene ether) of the present invention can further be used for protection from alpha particles and as a protective layer on integrated circuit chips. Semiconductor devices are prone to soft errors when alpha particles are released from a small amount of radioactive foreign material in packaging, or when other nearby materials stimulate the active surface. FIG. 3 is a schematic diagram of an integrated circuit having a protective layer of fluorinated poly (arylene ether). An integrated circuit chip 25 is disposed on a substrate 26 and is fixed at that position by an adhesive 27.
Fluorinated poly (arylene ether) coating 28
Becomes the alpha particle protective layer on the active surface of chip 25.
If necessary, it may be further protected by an encapsulant 29, for example made of epoxy or silicone.
The conductor 30 is connected between the chip 25 on the substrate 26 and a conductor (not shown) and to an external circuit.

Fluorinated poly (arylene ether) can also be used as a substrate (dielectric material) in circuit boards (also called printed interconnect boards or PWBs). FIG. 3a shows a circuit board 35 made of a substrate 36 having a pattern of conductors 37 on its surface.
FIG. Substrate 36 is made of the fluorinated poly (arylene ether) of the present invention. Substrate 36 may be reinforced with a non-conductive fiber fabric such as glass cloth. In FIG. 3a, the circuit board is shown on only one side, but as will be understood by those skilled in the art, fluorinated poly (arylene ether)
The substrate may have another structure such as a double-sided or multilayer structure.

The fluorinated poly (arylene ether) film or coating can be formed by a solution method such as a spray method, a spin coating method, or a casting method, but the spin coating method is preferable.
Preferred solvents are 2-ethoxyethyl ether, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, methyl isobutyl ketone, 2-methoxyethyl ether, 5-methyl-2-hexanone, γ-
Butyrolactone, and mixtures thereof. Typically, the thickness of the coating is from about 3 to about 15μ.

As is known in the polymer arts, additives such as stabilizers, flame retardants, pigments, plasticizers, surfactants and the like can be used to enhance or impart specific desired properties. Compatible or incompatible polymers can be mixed to achieve the desired properties.

Polymers used in electronic applications desirably contain low levels (typically less than 20 ppm) of ionic impurities.
If the polymer is prepared by a synthetic route that requires a transition metal reagent or catalyst, it is difficult to remove sufficient transition metal residues. An advantage of the present polymers is that they can be prepared in a route that does not require transition metal species, and potassium (or sodium) carbonate reagents and potassium (or sodium) fluoride by-products can be easily removed.

Fluorinated poly (arylene ether) exhibits good high temperature stability. For example, polymer (A) is 500 ℃ by TGA
Indicate initial weight loss in air. However, when heated above 300 ° C. in air, as indicated by the formation of large amounts of gelling material, it crosslinks unexpectedly. Preferably, the crosslinking temperature is from about 300 to about 425C. The presence of oxygen is necessary to carry out the crosslinking reaction, and a similar heating cycle in nitrogen will not form a gel. Due to this property, the fluorinated poly (arylene ether) can be readily applied from solution and then converted to a solvent resistant coating by heating in air, so that the fluorinated poly (arylene ether) It is particularly useful in the electronic applications described.

The fluorinated poly (arylene ether) has the formula: [Wherein -R ₁ , -R ₂ , -R ₃ and -R ₄ are independently-
H, alkyl of _{-C 6 H 5, -C 6 H} 4 Y ', or C ₁ ~C _4; -R
₅ -is -O-, -SO _2- , -B is -F, -Cl, -Br, -CH ₃ or -CF _3,; r is 0,
1, 2, 3 or 4,; -Y 'is halogen, -NO _2, -C ₆ H
₅ or C ₁ -C ₄ alkyl].

Preferably, -R _1, -R _2, each of -R ₃ and -R ₄ are,
Methyl and r is 0. Preferably, -R ₅ - is, It is. Further, Bisutoriazen group -R ₅ - preferably in the para position relative to the base.

Particularly preferred bistriazene crosslinkers are It is.

The bistriazene crosslinker has the formula: [Wherein -R _5- , -B and r are as defined above], prepared by treating a diamine solution (in a solvent such as tetrahydrofuran or methanol) with hydrochloric acid (slowly added, with stirring). it can. Next, the sodium nitrite solution is gradually added while cooling. After about 1 hour of reaction, the solvent is removed under reduced pressure. The residue is neutralized to pH 6-7 and treated with dihydrochloride of a diamine such as dimethylamine.

The bistriazene crosslinker is used in an amount sufficient to crosslink the fluorinated polymer, preferably about 10 to about 40% by weight, more preferably about 15 to about 30% by weight, based on the total weight of the polymer and the bistriazene compound. The fluorinated poly (arylene ether) and bistriazene compound are mixed homogeneously, preferably by solution mixing. A film of the mixture is formed, for example, by spin coating, and the solvent is removed. Crosslinking is performed by heating to a temperature above the decomposition temperature of the bistriazene compound, typically 300-400 ° C., and optionally stepwise heating, typically for a total time of about 15-90 minutes.

When heated above the critical temperature, the triazene group is considered to decompose to form a phenyl radical. These are then inserted into aromatic groups in the fluorinated poly (arylene ether) to form an aryl-aryl bridge as shown in the following formula: For the sake of simplicity, in the formula, the triazene group is shown to be decomposed to obtain a diradical at the same time. The decomposition may not be completely simultaneous and monoradicals are also formed, which react similarly but are sequential. Of note is that the bridge is through an aryl-aryl bond. Compared to aliphatic ones, they are less susceptible to thermal oxidation or other chemical attack and are therefore more stable.

Another method of crosslinking fluorinated poly (arylene ether) is dicumyl peroxide, cumene hydroperoxide,
Alternatively, a peroxide compound such as benzoyl peroxide is used. The homogenous mixture of the polymer and the peroxide compound is treated at about 350 ° C. to about 425 ° C., preferably about
Heat to a temperature of 400 ° C. Typically, the peroxide compound is used in an amount of about 5 to about 20% by weight based on the total weight of the polymer and the peroxide compound, with about 10% being preferred.
In some fluorinated poly (arylene ethers), peroxide crosslinking is promoted by its reactive side chain, for example, an allyl group in polymer (J), but the presence of such a functional group is effective. Not essential for peroxide crosslinking.

Fluorinated poly (arylene ethers) are also useful as adhesives and matrix resins in composite applications. Further, it is also useful as a solvent-resistant crosslinked film for various applications, for example, a crosslinked wire such as a wire having winding insulation.

The practice of the present invention will be further described by way of the following examples, which are intended to be illustrative and not limiting.

Example 1 This example describes the preparation of a polymer having repeating units (A): In a 500 ml round bottom flask, 1
5.01 g (0.0447 mol) of 4.4 '-(hexafluoroisopropylidene) diphenol (6F-diphenol), 15.2 g
9 g (0.0458 mol) of decafluorobiphenyl, 240 g of dimethylacetamide (DMAc) and 16.85 g (0.125 mol) of potassium carbonate were added. The mixture was heated with stirring at about 80 ° C. for 23 hours under a nitrogen atmosphere. The mixture was filtered hot to remove unreacted potassium carbonate and potassium fluoride by-products. About 75 ml of DMAc was removed by rotary evaporation. The solution was cooled to room temperature and poured into water to precipitate the polymer. Filter the polymer and add 3 with water
Washed twice, suspended in 200 ml of ethanol for 2 hours, filtered and dried at 100 ° C. for 2 hours to obtain a white powder. A solution of the polymer (2 g) in a mixture of 2-ethoxyethyl ether and cyclohexanone (50/50, 8 g) was spin-coated on a ceramic substrate, and the mixture was spin-coated at 100 ° C. for 15 minutes, 180 ° C. for 20 minutes, and 400 ° C. for 45 minutes. Dried for minutes. The resulting polymer film was tough, flexible, did not dissolve in 2-ethoxyethyl ether, and had a Tg by DSC of 189 ° C (192 ° C for TMA).

Example 2 This example describes the preparation of a polymer having repeating units (B): In a 100 ml round bottom flask, 2.
20 g (0.0118 mol) of hexafluorobenzene, 3.90 g
(0.0116 mol) of 6F-diphenol, 4.0 g (0.030 mol) of potassium carbonate, and 50 g of DMAc were added. The mixture was heated with stirring at about 70 ° C. under a nitrogen atmosphere for 48 hours. The mixture was then worked up as described in Example 1 to give a white powder. The resulting polymer film was tough, flexible, did not dissolve in 2-ethoxyethyl ether, and had a Tg by DSC of about 185 ° C.

Example 3 This example describes the preparation of a polymer having repeating units (C): 12.7 g of 4,4-isopropylidenebis (2,6-dimethylphenol) ("tetra Methyl bisphenol A ") and the reaction was carried out as in Example 1 except that the reaction was heated at 80 ° C. for 72 hours. 22.3 g of polymer were obtained. The moisture absorption of the obtained polymer film after immersion in water at 50 ° C. for 16 hours was 0.15%.

Example 4 This example describes the preparation of a copolymer having repeating units (A) and (N): 7.51 g of 6F-diphenol and 2.458 instead of 6F-diphenol
The reaction was the same as in Example 1 except that a mixture of g of resorcinol was used. 19.8 g of polymer were obtained. The moisture absorption of the obtained polymer film after immersion in water at 50 ° C. for 16 hours was 0.10%.

Example 5 This example describes the preparation of a polymer having repeating units (D): In a 250 ml round bottom flask, 1
0.15 g (0.029 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 9.97 g (0.0298 mol) of decafluorobiphenyl, 115 g of DMAc and 10.0 g (0.074 mol) of potassium carbonate were added. The mixture was heated with stirring at 75 ° C. under a nitrogen atmosphere for 16 hours. The mixture was cooled to room temperature and poured into vigorously stirred water to precipitate the polymer, filtered, washed twice with water, filtered and dried. A white fluffy powder was obtained. The white polymer powder (2 g) was dissolved in a mixture of cyclohexanone and 2-ethoxyethyl ether (50/50, 8 g). Approximately 1.5 ml of the polymer solution was spin-coated on a glass substrate,
Dry for 15 minutes at 400C and 30 minutes at 400C. The obtained polymer film was peeled off from the glass substrate by immersing it in water to obtain a tough, flexible and transparent film. The film had a dielectric constant of 2.62 at 0% RH and a dielectric constant of 2.68 at 58% RH. The Tg of the polymer by DSC was about 258 ° C.

Example 6 This example describes the preparation of a polymer having the repeating unit (E): Example 5 except that 5.54 g (0.0298 mol) of hexafluorobenzene was used instead of decafluorobiphenyl and the reaction was carried out for 42 hours. Operation 5 was repeated. The dielectric constant of the obtained polymer film is 0% RH
Was 2.65 and 58% RH was 2.73.

Example 7 This example describes the preparation of a copolymer having repeating units (A) and (D): In a 250 ml round bottom flask, 5.07 g (0.0145 mol) of 9,9-bis (4-hydroxyphenyl) ) Fluorene, 4.87 g (0.0145 mol)
6F-diphenol, 9.97 g (0.0298 mol) of decafluorobiphenyl, 115 g of DMAc and 10.0 g (0.074 mol)
Of potassium carbonate was added. The mixture was heated with stirring at about 75 ° C. under a nitrogen atmosphere for 16 hours. The mixture was cooled to room temperature and poured into vigorously stirred water to precipitate the polymer, filtered, washed twice with 300 ml of water, filtered and dried. A white fluffy powder was obtained. White polymer powder (2g)
Was dissolved in a mixture of cyclohexanone and 2-ethoxyethyl ether (50/50, 8 g). About 1.5 ml of the polymer solution is spin-coated on a glass substrate,
Dried at 200 ° C. for 15 minutes and 400 ° C. for 30 minutes. The obtained polymer film was peeled from the glass substrate by immersion in water to obtain a tough, flexible, transparent film. The dielectric constant of this film is 2.60 and 58% at 0% RH
RH was 2.66.

Example 8 This example describes the preparation of a polymer having repeating units (F): In a 100 ml round bottom flask, 3.
50 g (0.0208 mol) of pentafluorobenzene, 7.00 g
(0.0208 mol) of 6F-diphenol, 4.2 g of potassium carbonate, and 50 g of DMAc were added. The mixture is heated with stirring at about 80 ° C. for 24 hours under a nitrogen atmosphere and at 120 ° C. for a further 3 hours.
Heated for 6 hours. The mixture was cooled to room temperature and poured into water, whereupon a slightly colored powdery polymer precipitated. The polymer was washed three times with water and dried at room temperature for 18 hours and at 100 ° C. for 4 hours. The polymer (1 g) was dissolved in a 1: 1: 1 mixture of DMAc, 2-ethoxyethyl ether and cyclohexanone (4 g). The mixture is spin-coated on a glass substrate,
After curing at 100 ° C. for 15 minutes, 200 ° C. for 15 minutes and 400 ° C. for 15 minutes, an amber film was obtained. The moisture absorption of the polymer was 0.15%. More specifically, based on a model experiment with a similar fluorinated benzene described later and the mechanism of the expected polymerization reaction, it is considered that two fluorines in pentafluorobenzene are substituted and hydrogen remains. DS of polymer (F)
The Tg by C was 120 ° C.

Example 9 This example describes the preparation of a polymer having repeating units (G): using 4.99 g (0.0211 mol) of octafluorotoluene instead of pentafluorobenzene and 7.38 g instead of 6F-diphenol. (0.0211
Mol) of 9,9-bis (4-hydroxyphenyl) fluorene. The reaction was carried out at 80 ° C. for 24 hours and then at 120 ° C. for another 24 hours.
A white powder was obtained. Here too, it is considered that the fluorine of the two rings is substituted and the trifluoromethyl group remains. The Tg of the obtained polymer determined by DSC was 260 ° C.

Example 10 This example describes the preparation of a polymer having repeating units (H): Example 9 except that 6.40 g (0.0208 mol) of 1,4-dibromotetrafluorobenzene was used instead of octafluorotoluene. The method was the same. A white powder was obtained. 1 g of the powder was dissolved in 4 g of DMAc, spin-coated on a glass substrate, and cured in the same manner as in Example 8 to obtain an amber film. The dielectric constant of the polymer was 2.6 and the moisture absorption was 0.15%. Tg was 199 ° C. as measured by DSC.

GC of the product obtained from the model reaction between phenol (2 equivalents) and 1,4-dibromotetrafluorobenzene
-MS analysis showed that two fluorines were substituted, two bromines remained and a mixture of isomer products was obtained. Therefore, it is considered that two bromines remain in the polymer (H).

Example 11 This example describes the preparation of a polymer having repeating units (I): In a 100 ml round bottom flask, 5.
05 g (0.0249 mol) of chloropentafluorobenzene,
9.10 g (0.026 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 65 g of DMAc and 11.5 g of potassium carbonate were added. While stirring the mixture under a nitrogen atmosphere,
Heated at 100 ° C. for 27 hours. The mixture was cooled to room temperature and poured into water with stirring to precipitate the polymer. The polymer was washed three times with water and dried at room temperature for 18 hours and at 100 ° C. for 5 hours to obtain a white powder. The polymer (2 g) was mixed with a mixture of 2-ethoxyethyl ether and cyclohexanone (1: 1, 8
ml), spin-coated on a glass substrate, and dried as in Example 8. An amber film was obtained. The moisture absorption of the polymer was 0.1%.

According to GC-MS analysis of the product obtained from the model reaction between phenol (2 equivalents) and chloropentafluorobenzene, two fluorines have been replaced, chlorine has remained and the mixture of isomer products It turned out to be obtained. Therefore, it is considered that chlorine remains in the polymer (I).

Example 12 This example describes the preparation of a polymer having repeating units (J): In a 100 ml round bottom flask, 4.
20 g (0.0202 mol) of allylpentafluorobenzene,
6.85 g (0.0204 mol) of 6F-diphenol, 45 ml of DMAc
And 8.0 g of potassium carbonate were added. The mixture was heated with stirring to about 110 ° C. under a nitrogen atmosphere for 72 hours. The mixture was cooled to room temperature and poured into water to precipitate the polymer. The polymer was washed with 100 ml of deionized water and 100 ml of denatured ethanol and dried in air for 3 days to obtain a pale yellow powder. Powder (3 g) and 0.15 g of t-butyl perbenzoate were dissolved in 8.5 ml of DMAc, spin-coated on a glass substrate, dried at 110 ° C. for 10 minutes, and dried at 200 ° C. for 20 minutes,
An amber film that did not dissolve in DMAc was obtained.

According to GC-MS analysis of the product obtained from the reaction between phenol (2 equivalents) and allylpentafluorobenzene, two fluorines were substituted, the allyl group remained, and the mixture of isomer products was obtained. It turned out to be obtained. Therefore, it is considered that allyl groups remain in the polymer.

Example 13 This example describes the preparation of a polymer having repeating units (K): 1. In a 100 ml round bottom flask, 1.
25 g (0.0042 mol) of 2,2 ', 3,3', 5,5 ', 6,6'-octafluorobiphenyl (OFB), 1.41 g (0.0042 mol) of 6F
-Diphenol, 19 g of DMAc and 2 g of potassium carbonate were added. 120 ° C under a nitrogen atmosphere while stirring the mixture
For 72 hours. The mixture was cooled to room temperature and poured into water to precipitate the polymer. The polymer was collected by filtration, washed with a 50/50 mixture of ethanol and water (75 ml) and dried overnight at room temperature and then at 100 ° C. for 1 hour to give a white powder.
The Tg of the polymer determined by DSC was 147 ° C.

According to GC / MS analysis of the product obtained from the reaction between 4-methoxyphenol (2 equivalents) and OFB, two fluorines were substituted, two hydrogens remained and the isomer product It was found that a mixture was obtained. Therefore, it is considered that two hydrogens remain in the polymer.

Example 14 This example describes the preparation of a polymer having repeating units (L): 6.22 g (0.0202 mol) of 1,4
The procedure was as in Example 12, except that -dibromotetrafluorobenzene, 7.07 g (0.0202 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 10 g of potassium carbonate and 55 ml of DMAc were used. A white powder polymer was obtained. Tg by DSC was 291 ° C.

Example 15 This example describes the preparation of a polymer having repeating units (M): 1 in a 250 ml round bottom flask
0.2 g (0.0354 mol) of 4,4 '-(1-phenylethylidene) bisphenol, 11.6 g (0.0347 mol) of decafluorobiphenyl, 12 g of potassium carbonate and 135 g of DMA
c was added. 80 ° C under a nitrogen atmosphere while stirring the mixture
For 16 hours. The mixture was cooled to room temperature and poured into water, causing the polymer to precipitate. The polymer was filtered, washed with water and dried. The polymer (2 g) was dissolved in an 8: 2 mixture of 2-ethoxyethyl ether and cyclohexanone (8 g), spin-coated on a glass substrate,
After drying at 200 ° C. for 15 minutes and at 400 ° C. for 15 minutes, a flexible and transparent film was obtained. The Tg of the polymer at 208 ° C. by DSC was 0
The dielectric constant at% RH was 2.64.

Example 16 In this example, the repeating units (A) and (O)
The preparation of a copolymer having a molar ratio of 1: 4 is described: In a 100 ml round bottom flask, 3.75 g (0.021 mol) of 4,6
-Dichlororesorcinol, 1.76 g (0.0053 mol) of 6F
-Diphenol, 8.80 g (0.026 mol) of decafluorobiphenyl, 62 g of DMAc and 10 g of potassium carbonate were added. The mixture was heated to 110 ° C. under a nitrogen atmosphere for 8 hours. The mixture was poured into water without cooling to precipitate the polymer.
The polymer was collected by filtration, washed with water, and dried to give a pale pink powder. The Tg of the polymer determined by DSC was 149 ° C.

Example 17 This example describes the preparation of a polymer obtained from 4,4'-isopropylidene diphenol and decafluorobiphenyl (hereinafter BPA-DFB): 10.20 g instead of 6F-diphenol The procedure of Example 1 was repeated except that 4,4'-isopropylidene diphenol (bisphenol A) was used. The reaction yielded 21.5 g of polymer. Polymer water in 50 ° C water
The moisture absorption after immersion for 16 hours was 0.2%.

Example 18 This example is a comparative example, wherein the repeating unit is: A non-inventive polymer having the formula is prepared and compared with the inventive polymer.

In a 100 ml round bottom flask, 1.80 g (0.009 mol) of 4,4 '
-Oxydianiline (ODA) and 30 ml of dry 1-methyl-2-pioridinone (NMP) were added. The solution was cooled in an ice bath and stirred under a nitrogen atmosphere with 2.006 g (0.00
(92 mol) pyromellitic anhydride (PMDA) was added.
A viscous amber solution was obtained. About 10x10c of polymer solution
spin-coated on a 4x4 inch glass substrate,
Drying at 10 ° C. for 10 minutes, 200 ° C. for 15 minutes, and 350 ° C. for 30 minutes gave an amber film. The moisture absorption after immersing the film in water at 50 ° C. for 16 hours was 2.55%.

Example 19 This example is another comparative example, in which another polyimide of the prior art, referred to herein as P17, is prepared and compared to the polymer of the present invention: In a 100 ml round bottom flask, add 3.35 g (0.009 mol) of 4,4 '
-Bis (4-aminophenoxy) biphenyl and 17 g
Of NMP was added. After stirring at room temperature under a nitrogen atmosphere for 45 minutes, a solution of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) (4.00 g, 0.009 mol) in NMP (14 g) was stirred. While dropping over 10 minutes. After stirring at room temperature for another 24 hours, a viscous solution (2650
cps). Spin-coat the solution on a 4x4 inch glass substrate, 100xC for 30 minutes, 200xC
After drying for 20 minutes at 350 ° C. for 30 minutes, an amber film was obtained. The bulk moisture absorption after immersing this polyimide film in water at 50 ° C. for 16 hours was 0.85%. In Table I
The properties of p17 are compared with those of the polymer of the invention.

Table I compares the dielectric properties of the polymers of the present invention with those of the comparative examples. US Patent Application No. 07 / 447,771 pending at 25 ° C, 10KHz (Mercer)
The measurement was carried out according to the method described in 1. As can be seen from Table I, the ε of the control polymer is greater than 2.80 and up to 3.16, whereas the polymers of the invention are significantly lower, ie 0%
It has a dielectric constant (ε) of less than 2.80 at RH and at least 2.50. Further, the ε of the polymers of the present invention is not sensitive to changes in ambient humidity. At about 60% RH, ε rises slightly as seen in the small slope between 10 and 30, while the control polymer has about 60
And a slope between about 100. In electronic articles, it is important that the dielectric material have a low ε, preferably less than 3 in both dry and wet environments. The differences between the inventive polymer and the control polymer are graphed in FIG.

Example 20 This example describes the fabrication of a multilayer high density interconnect article suitable for use in a multi-chip module or with a single integrated circuit chip.

A solution of polymer (A) (22.5 g) in a 50/50 mixture (77.5 g) of 2-ethoxyethyl ether and cyclohexanone was prepared. The polymer insulation layer was applied on the ceramic substrate in the following manner: (1) The polymer solution (5 ml) was spin coated on a clean 125 mm diameter ceramic substrate. (2) Coating at 200 ° C for 15 minutes at 100 ° C
Dried for 15 minutes. (3) Further, 5 ml of the solution was applied and cured at 400 ° C. for 60 minutes, followed by curing as described above. A conductive material was formed by blanket sputtering 200 ° chromium, followed by 5 micron copper, and finally another 500 ° chromium. The metal was photolithographically patterned.

A second polymer insulating layer was applied over the patterned metal layer by the three-step method as described above. An aluminum metal layer was formed by blanket sputtering on the dielectric, photolithographically patterned, formed vias in the second dielectric layer, and made electrical connections to the first metal layer. The aluminum layer was removed. A second metal layer of chromium / copper / chromium was applied as described above and vias made electrical connections with the first layer. Next, the second metal layer was patterned photolithographically.

All metal layers in the device exhibited excellent adhesion to the fluoropolymer, with no delamination between metal / polymer or between polymers.

Example 21 The sample polymer (A) was crosslinked by curing in air at the times and temperatures shown in Table II below to give the indicated gel content (determined by Soxhlet extraction with DMAc for 24 hours). .

However, the polymer (A) was placed in nitrogen at 300 ° C. for 13 minutes,
Next, when cured at 400 ° C. for 27 minutes, no gel was detected.

Example 22 This example illustrates the preference of fluorination at the bisphenol group for the preparation of fluorinated (arylene ether) with improved thermal stability. Polymer (A) (6F
-Derived from diphenol and having two -CF ₃ groups) by thermogravimetric analysis under isothermal conditions in air (TGA)
The polymer BPA-DFB (derived from bisphenol-A,
Therefore, two --CH ₃ groups are present at the corresponding positions). The results are shown in Table III.

Example 23 This example describes the deposition of a polymer (D) layer crosslinked with a bistriazene crosslinker. Solution of polymer (D) in a solvent system of bis (2-ethoxyethyl) ether, DMAc and 5-methyl-2-hexanone (1: 1: 1 (W / W / W)) (solids content about 23% by weight) ) Was prepared. 16.7% by weight
Bistriazene (1): Was added. This solution was then coated on a substrate (ceramic or silicon) by spin coating. The coated substrate was heated in an oven purged with nitrogen.
This oven has a conveyor belt, which allows the substrate to move in the oven at a temperature distribution of 300 ° C for 6.5 minutes and 400 ° C for 13.5 minutes.
Minutes, then 20 minutes to cool to room temperature.
In this way, a transparent coating of the crosslinked polymer (D) was obtained, which did not crack by further processing (for example during the deposition of another polymer layer) and did not cause oxidation of the metal conductor thereon.

In order to improve the adhesion of the crosslinked polymer (D) to the substrate, a thin layer containing a polyimide having an acetylene terminal (Thermid IP-615) and a γ-aminopropyltrimethoxysilane coupling agent ( Polymer (D) having a thickness of about 1μ) as an adhesion promoting intermediate layer
It is desirable to use it between the substrate and the substrate. A polyimide / coupling agent layer is deposited on the substrate, at 150 ° C. for 10 minutes, and then
Cured at 00 ° C. for 15 minutes. A layer of polymer (D) was then coated on top and cured as described above.

Example 24 In this example, the polymer (D) described in the previous example was used.
Describes metallization, patterning, etching and via formation on substrates coated with.

A trace amount of metal conductor was deposited on the cured polymer (D) coating by sputtering. The conductor had a chromium-copper-chromium sandwich structure in which a 200 mm thick chromium layer served as a tie-down layer of copper (5 μm thick). This conductor structure is preferred over the more common aluminum which does not adhere much to the crosslinked polymer (D).

The metal was coated with a photoresist, which was then coated with a mask and exposed to UV light. The exposed portions of the photoresist were removed by washing with a sodium hydroxide solution, exposing the metal portions. The exposed metal was removed by removing the top chromium and copper layers, respectively, by etching with CRE-473 (trademark of hydrochloric acid etchant, available from Transene) and ferric chloride. The bottom chromium layer was removed by etching with CE8001-N (trademark of cerium ammonium nitrate-nitric acid etchant, available from Chemtech Industries). Laser ablation can also be used to remove the bottom chrome layer,
CE8001-N is preferred because it acts quickly and gives less roughness to the polymer.

After etching the metal, the entire substrate wafer was exposed to ultraviolet light, and the remaining photoresist was removed by developing it with sodium hydroxide. Alternatively, undeveloped photoresist may be treated with NMP, deionized and methanol (7: 3: 1 (V / V /
V)) can be removed with the mixture.

The patterned metal was further overcoated with a crosslinked polymer (D). A metal layer or via mask (3μ thick) was sputtered onto the polymer coating and photolithographically patterned as described above to form holes in the metal where vias were desired. All wafers
Fusion was performed with a 308 nm laser to remove the polymer with holes in the metal until it reached the metal at the bottom. The mask was then etched away (the via mask must be made of a different, selectively etchable metal, such as aluminum, to avoid etching the metal conductors with the via mask).

A substrate wafer having a plurality of multilayer units was prepared using the method described above. A schematic diagram of this substrate and the units thereon is shown in FIG. 5 (numbers indicate elements). The substrate 40 has a plurality of multilayer units 41 (shown in an enlarged top view and a sectional view) thereon. Each unit 41 has metal conductor layers 43a and 43b exposed by a dielectric 42 of a crosslinked polymer (D). Vias 44a and 44b connect the layers. Each unit 21 can be considered as a parallel plate condenser. Twenty units 41 were tested by measuring their capacitance. Each has the formula: C = D _εo A / L [where C is the capacitance, D is the dielectric constant of the polymer interlayer, _εo is the dielectric constant of free space, A is the area of the capacitor plate, and L is the distance between the capacitor plates. Which had a capacitance consistent with the value expected by (The distance between the capacitor plates (i.e., the conductor layers) was measured with a scanning electron microscope to be 35 μm.) Example 25 In this example, the dielectric properties of the polymer (D) crosslinked with bistriazene in the method of Example 23 were determined by Compare the dielectric properties of a benzocyclobutene (BCB) resin (XU 13005.02L, available from Dow Chemical Company) proposed as a dielectric for electronic packaging. Capacitors were prepared according to the method of Example 24 from crosslinked polymer (D) and BCB resin.
The capacitance of five capacitor pieces made from each polymer was measured as a function of% RH before and after aging. The results are shown in Table IV.

From these results, it is understood that the dielectric properties of the crosslinked polymer (D) are not inferior to those of the BCB resin. Although the initial dielectric constant of the BCB resin is low, the dielectric constant of the BCB resin increased considerably sharply, especially at high% RH, due to the high temperatures experienced during the normal service life of electronic articles. . In contrast, the dielectric constant of polymer (D) remained lower than 2.8 for all aging time-relative humidity combinations.

Example 26 This example illustrates the crosslinking of various fluorinated poly (arylene ethers) with various bistriazene crosslinkers.

Fluorinated poly (arylene ether) sample (2
g) in a 30 ml vial, cyclohexanone (4 g), γ
-Butyrolactone (4 g), a bistriazene compound (approx.
4g) and a surfactant (Fluorad FC-43)
1, 2M). The mixture was stirred until all solids were dissolved. The solution was allowed to settle until all the foam created by the stirring had dissipated. Most of the solution was deposited on a ceramic substrate and spin coated at 250 rpm to form a thick coating. Sample at 100 ° C for 15
And then soft baked at 200 ° C. for another 15 minutes. The sample was then baked in a nitrogen purged furnace according to the following cycle to yield about 1.5 g sample: 300 ° C
6.5 minutes, 400 ° C for 13.5 minutes, room temperature for 20 minutes.

Remove the cured sample from the ceramic substrate
Divided into two equal parts. Each part was cut into small pieces and placed in pre-weighed graduated test tubes. The graduated test tube was sealed and weighed again. All three parts were charged into a Soxhlet extractor and extracted with DMAc for 24 hours. After drying in a vacuum oven at 100 ° C. overnight, the samples were cooled and weighed again to determine the gel content. From the results shown in Table V, it is understood that the bistriazene compound is generally effective as a crosslinking agent for fluorinated poly (arylene ether).

Example 27 In this example, fluorinated poly (arylene ether) D is cross-linked with a peroxide compound. A sample of Polymer D containing 10% dicumyl peroxide or cumene hydroperoxide was placed in an infrared oven at 300 ° C. under a nitrogen atmosphere.
For 6.5 minutes and then at 400 ° C. for 13.5 minutes to obtain a crosslinked polymer having a gel content of 94.0% and 81.4%, respectively. In the comparative example, the gel content of the polymer D sample similarly heated in the absence of peroxide was only 3.3%.

The crosslinked polymer retained its low moisture absorption and dielectric properties. The moisture absorption of the sample crosslinked with dicumyl peroxide is
0.2% and a dielectric constant of 2.6 at 0% RH.

In another peroxide cross-linking experiment, polymers (A) and (D) were cross-linked with 10% by weight of benzoyl peroxide, respectively, to give cross-linked polymers with gel contents of about 51 and 49%, respectively. Crosslinking of polymer (A) with 10% by weight of dicumyl peroxide resulted in a gel content of 69%. For comparison, the gel content of a control sample of polymer (A), also heated in the absence of peroxide, was about 0.8%.

Example 28 This example describes the preparation of a polymer having repeating units (M '): 3.21 g in a 100 ml round bottom flask
(0.0093 mol) of bisphenol P, 3.12 g (0.00934 mol) of decafluorobiphenyl, 4.2 g of potassium carbonate and 22 g of DMAc were added. The reaction mixture was heated at 100 ° C. for 6 hours with stirring under a nitrogen atmosphere. The polymer was isolated as described in Example 5 to give a white powder. The Tg of the polymer determined by DSC was 162 ° C. The dielectric constant of the polymer film is 2.58 at 0% RH and 2.71 at 66.45% RH
Met.

Example 29 This example describes the preparation of a copolymer having repeating units (A) and (O): In a 100 ml round bottom flask, 3.75 g (0.026 mol) of 4,6-dichlororesorcinol, 1.76 g (0.0052 Mol) 6F-diphenol, 10.45 g
(0.031 mol) of decafluorobiphenyl, 12 g of potassium carbonate and 39 g of DMAc were added. The reaction mixture was heated at 110 ° C. for 8 hours with stirring under a nitrogen atmosphere. The gelation reaction mixture was cooled to room temperature, added to water and digested in a blender to isolate an off-white powder. The powder was washed with water and dried. Tg of polymer at 149 ° C by DSC
Met.

Example 30 This example describes the preparation of a copolymer having repeating units (A) and (P): In a 100 ml round bottom flask, 5.70 g (0.017 mol) of decafluorobiphenyl, 1.
34 g (0.0083 mol) of 2,7-dihydroxynaphthalene, 2.
82 g (0.0083 mol) of 6F-diphenol were added. The reaction mixture was heated to 90 ° C. with stirring under a nitrogen atmosphere for 18 hours and cooled to room temperature. The polymer was isolated as described in Example 5 to give a white powder. The Tg of the polymer determined by DSC was 190 ° C. The dielectric constant of the polymer film was 2.54 at 0% RH and 2.64 at 65.4% RH.

Example 31 This example describes the preparation of a copolymer having repeating units (A) and (Q): 1.34 g (0.0083 mol)
Example 30 was repeated except that 1,5-dihydroxynaphthalene was used instead of 2,7-dihydroxynaphthalene. An off-white powder was obtained. T of polymer by DSC
g was 203 ° C.

Example 32 This example describes the preparation of a copolymer having repeating units (D) and (Q) and subsequent crosslinking with peroxide: In a 250 ml round bottom flask, 3.32 g (0.020
7 mol) of 1,5-dihydroxynaphthalene, 7.26 g (0.020
7 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 14.22 g (0.0427 mol) of decafluorobiphenyl, 17 g of potassium carbonate and 127 g of DMAc were added.
The reaction mixture was heated at 85 ° C. with stirring under a nitrogen atmosphere for 16 hours, then poured hot into a blender containing 300 ml of water to precipitate the polymer. Filter the polymer,
Washed twice with 300 ml of water and dried. 2g of polymer and
0.22 g of dicumyl peroxide was dissolved in 8.5 g of a 1: 1 mixture of gamma-butyrolactone and cyclohexanone. The solution was spin coated on a ceramic substrate and cured as follows: 30 minutes at 130 ° C., 400 at a rate of 5 ° C./min.
C., kept at 400.degree. C. for 15 minutes and cooled to room temperature at a rate of 3.degree. C./min. An amber film was obtained, which was γ-
When exposed to a butyrolactone-cyclohexanone mixture, it did not stress crack or dissolve. A control copolymer film, also heated under a nitrogen atmosphere without the addition of dicumyl peroxide, exhibited solvent-induced stress cracking when exposed to a similar solvent mixture.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI H01L 21/768 H01L 21/90 S 23/12 23/30 R 23/29 23/12 N 23/31 (31) Claiming priority No. 583,900 (32) Priority date September 17, 1990 (September 17, 1990) (33) Priority country United States (US) (72) Inventor Goodman, Timothy Dee United States 94062 California, Red Wood City, Oak Nor 3627 (72) Inventor Rho, Aldrich N.K.USA 94303 California, Palo Alto, Amarillo Avenue 1067 (72) Inventor Vaud, Ranchi P United States 95148 California A, San Jose, Deerwood Drive 2831 (72) Inventor Sovish, Li Chard Sea United States 94133 California, Los Altos, Lockhart Lane 125 No. (56) Reference JP-A-2-281031 (JP, A) JP-A-2-153930 (JP, A) JP-A-2 -4829 (JP, A) JP-A-61-47710 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08G 65/00-65/48

Claims (11)

(57) [Claims] 1. The formula: [Wherein -W- is [However, each -A is independently -F, -Cl, -Br, -C
F _3, -CH _3, be -CH ₂ CH = CH ₂ or -C ₆ H _5; p is 0,
1 or 2; -Z- is a direct bond, -C (CH ₃ ) _{2
-, - C (CF 3)} 2 -, - O -, - S -, - SO 2 -, - CO
_{-, - P (C 6 H} 5) -, - C (CH 3) (C 6 H 5) -, - C (C
_{6 H 5) 2 -, -} (CF 2) 1~6 - or (Where -Y- is -O- or a direct bond); and m is 0, 1 or 2, but when m is 0, -Z- is a direct bond. It represents; each -X is independently, -H, -Cl, -Br, -CF 3, -CH 3,
Represents -CH ₂ CH = CH ₂ or -C ₆ H _5; q is 0, 1 or 2
And n is 1 or 2.] An electronic article comprising, as a dielectric material, a fluorinated poly (arylene ether) having a repeating unit having the structure represented by the following formula: 2. A multi-chip module comprising a substrate, a plurality of semiconductor chips on the substrate, and a multi-layer interconnect connecting the semiconductor chips, wherein the multi-layer interconnection is a fluorine as defined in claim 1. The electronic article according to claim 1, comprising a plurality of dielectric material layers made of functionalized poly (arylene ether) and a plurality of conductive material layers. 3. A plurality of dielectric materials comprising an integrated circuit chip and a multilayer interconnect on said chip, said multilayer interconnect comprising a fluorinated poly (arylene ether) as defined in claim 1. The electronic article according to claim 1, comprising a layer and a plurality of conductive material layers. 4. An electronic article according to claim 1, which is an integrated circuit chip having a protective layer thereon, said protective layer comprising a fluorinated poly (arylene ether) as defined in claim 1. 5. An electronic article according to claim 1, which is a circuit board having a substrate having a conductor pattern on its surface, said substrate comprising a fluorinated poly (arylene ether) as defined in claim 1. 6. In a fluorinated poly (arylene ether), -W- is The electronic article according to any one of claims 1 to 5, wherein 7. The fluorinated poly (arylene ether) The electronic article according to any one of claims 1 to 5, wherein 8. The method according to claim 1, wherein the dielectric material is The electronic article according to any one of claims 1 to 5, comprising a fluorinated poly (arylene ether) having a repeating unit having the following structure: 9. The fluorinated poly (arylene ether)
formula: [Wherein -R ₁ , -R ₂ , -R ₃ and -R ₄ are independently-
H, -C ₆ H _5, an alkyl of -C ₆ H ₄ Y 'or _{C 1~4;} -R ₅ - is -O -, - SO ₂ -, -B is -F, -Cl, -Br, be -CH ₃ or -CF _3; r is 0, 1, 2, 3 or 4; -Y 'is halogen, -
NO _2, -C ₆ H ₅ or C ₁ -C ₄ electronic article according to claim 1 in Bisutoriazen compound represented by alkyl as] is crosslinked. 10. A fluorinated poly (arylene ether)
The electronic article according to any one of claims 1 to 5, which has been crosslinked by heating at a temperature of 300 to 400C in air. 11. A fluorinated poly (arylene ether)
The electronic article according to any one of claims 1 to 5, wherein the is crosslinked by heating a homogeneous mixture with a peroxide compound in air.