POLYARYLENE COMPOSITIONS AND METHODS

Abstract

Polyarylene oligomer compositions having improved adhesion to surfaces as compared to conventional polyarylene oligomers are useful in forming dielectric material layers in electronics applications.

Claims

1. A composition comprising: one or more polyarylene polymers comprising as polymerized units one or more polyalkynyl-substituted aryl first monomers and one or more biscyclopentadienone second monomers, the one or more polyarylene polymers having a backbone comprising as repeating units one or more aryl moieties having one or more adhesion promoting moieties.

2. The composition of claim 1 wherein the adhesion-promoting moiety improves adhesion of the polyarylene oligomer to an inorganic surface.

3. The composition of claim 1 wherein the adhesion-promoting moiety comprises an electron-donating atom at least 3 atoms away from the aryl moiety.

4. The composition of claim 3 wherein the electron-donating atom is chosen from O, N, S, and P.

5. The composition of claim 4 wherein the adhesion-promoting moiety comprises one or more adhesion-promoting substituents chosen from epoxy groups, hydroxy groups, ether groups, ester groups, keto groups, siloxy groups, amino groups, imino groups, phosphine groups, phosphite groups, phosphine oxide groups, phosphonate groups, and phosphate groups.

6. The composition of claim 5 wherein the one or more adhesion-promoting substituents are chosen from are epoxy groups; hydroxy groups; carboxy groups; ester groups; siloxy groups; and amino groups

7. The composition of claim 1 further comprising one or more crosslinkers.

8. The composition of claim 7 wherein the one or more crosslinkers is chosen from polyamine compounds, polyepoxide compounds, and polyhydroxy compounds.

9. The composition of claim 1 further comprising one or more organic solvents.

10. The composition of claim 1 wherein at least one polyalkynyl-substituted aryl first monomer has the formula ##STR00019## wherein Ar.sup.1 and each Ar.sup.2 are independently a C.sub.5-30-aryl moiety; each R.sup.1 is independently chosen from H, C.sub.5-30-aryl, and substituted C.sub.5-30 aryl; each R.sup.2 is independently chosen from C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, C.sub.1-10-alkoxy, CN, and halo; each Z is an adhesion-promoting moiety; Y is a chemical bond or a divalent linking group chosen from O, S, S(O), S(O).sub.2, C(O), (C(R.sup.5).sub.2).sub.z, C.sub.5-30-aryl, and (C(R.sup.5).sub.2).sub.z1(C.sub.5-30 aryl)-(C(R.sup.5).sub.2).sub.z2; each R.sup.5 is independently chosen from H, hydroxy, halo, C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, and C.sub.5-30-aryl; a1=0 to 3; each a2=0 to 3; b1=1 to 4; each b2=0 to 2; c1=0 to 2; each c2=0 to 2; a1+a2+a2=1 to 6; b1+b2+b2=2 to 6; c1+c2+c2=0 to 6; d=0 to 2; z=1 to 10; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10.

11. The composition of claim 10 wherein each Z has the formula (2)
*-LGAPS).sub.w(2) wherein LG is a linking group; each APS is an adhesion-promoting substituent comprising one or more electron-donating atoms chosen from O, N, S, and P; w is an integer from 1 to 6; and * is the point of attachment to an aryl moiety; wherein LG is selected such that at least one electron-donating atom of the adhesion-promoting substituent is at least 3 atoms away from the aryl moiety.

12. A method comprising: providing a substrate; coating a layer of the composition of claim 1 on a surface of the substrate; and curing the layer of the composition.

13. The method of claim 12 wherein the layer of the composition is cured by heating.

Description

EXAMPLE 1

[0049] To an oven-dried single-necked 1000 mL round-bottomed flask containing a stir bar, 3,5-diethynylbenzoic acid (DEBzOH, 10.00 g, 58.76 mmol) and dimethylformamide (DMF, 0.04 g, 0.59 mmol) were added via powder funnel, followed by dichloromethane (250 mL). The reaction was stirred gently at room temperature under a flowing blanket of nitrogen for 20 minutes before cooling in an ice water bath for 30 minutes. Oxalyl chloride (8.15 g, 64.64 mmol) was added dropwise via syringe, and the clear, light orange reaction mixture turned dark brown and opaque. The mixture was allowed to warm to room temperature as the ice bath melted. After stirring overnight, the stir bar was removed from the flask, and the solvent was removed by rotary evaporation. The dark, viscous mixture was further concentrated on a vacuum line to remove any residual oxalyl chloride, during which time the mixture solidified. A stir bar was added, the contents of the flask were re-dissolved in dichloromethane (250 mL), and a liquid addition funnel was attached to the flask. The vessel was again cooled in an ice water bath for 20 minutes. Simultaneously, a separate oven-dried 500 mL round-bottomed flask with a stir bar was charged with dimethylaminopyridine (DMAP, 0.07 g, 0.59 mmol) and dichloromethane (250 mL) before triethylamine (17.79 g, 176.29 mmol) and glycidol (4.79 g, 64.64 mmol) were added by syringe, and this mixture was allowed to stir at room temperature under nitrogen while the adjacent flask was cooling. The contents of this second flask were transferred to the addition funnel, and added to the cooled flask over 1 hour. This flask was allowed to warm to room temperature over 2 hours, and then stirred for another 24 hours. The reaction was stopped by adding 500 mL of water and extracting with two portions of 250 mL dichloromethane. The combined organic layers were washed with saturated aqueous sodium chloride, dried over sodium sulfate, and filtered. Concentration of the eluent yielded a brown solid, which was suspended on silica gel and separated using a CombiFlash automated purification system and an ethyl acetate/heptanes solvent system to furnish 3,5-diethynylbenzoic acid glycidyl ester (DEBzOH-GE) as a pale yellow solid (8.77 g, 38.78 mmol, 66% yield). The structure of the monomer was confirmed by .sup.1H and .sup.13C NMR. The reaction is illustrated in Scheme 2.

##STR00015##

EXAMPLE 2

[0050] To an oven-dried single-necked 500 mL round-bottomed flask containing a stir bar, DEBzOH (2.01 g, 11.81 mmol) and hexa(ethylene glycol) (10.09, 35.42 mmol) were added before the addition of toluene solvent (350 mL) and p-toluenesulfonic acid catalyst (0.01 g, 0.07 mmol). A large excess of hexa(ethylene glycol) was used to prevent dimerization. A Dean-Stark trap and reflux condenser with chilled water were affixed to the top of the flask, and the mixture was heated with an aluminum heating block to an external temperature of 140 C. under a flowing blanket of nitrogen. The reaction was stirred at this temperature for 48 hours, during which time water collected in the bottom of the trap. After this period, the reaction was cooled, and the contents were added to 300 mL ethyl acetate, and washed with five 500 mL portions of water. The organic layer was washed again with saturated aqueous sodium chloride, dried over sodium sulfate, and filtered. Concentration of the eluent yielded an orange solid, which was suspended on silica gel and separated using a CombiFlash automated purification system and an ethyl acetate/heptanes solvent system to furnish 3,5-diethynylbenzoic acid hexa(ethylene glycol) ester (DEBzOH-HEG) as a pale yellow solid (2.2 g, 5.01 mmol, 42% yield). The structure of the monomer was confirmed by .sup.1H and .sup.13C NMR. The reaction is illustrated in Scheme 3.

##STR00016##

EXAMPLE 3

[0051] To a multineck round-bottomed flask containing a stir bar, diphenylene oxide bis(triphenylcyclopentadienone) (DPO-CPD, 3.15 g, 4.02 mmol) and DEBzOH-GE (1.00 g, 4.42 mmol) from Example 1 were added via powder funnel, followed by PGMEA (40 mL). The reaction was stirred gently at room temperature. The flask was next equipped with a reflux condenser and an internal thermocouple probe attached to a self-regulating thermostat control for a heating mantle. Next, the dark maroon contents of the flask were warmed to an internal temperature of 110 C. and maintained at this temperature for 72 hours before cooling to 25 C. by removal of the heating element. The resulting maroon solution was precipitated from PGMEA using 500 mL isopropyl alcohol as an antisolvent. Filtration and drying of the precipitate under vacuum overnight yielded Polymer 1 as a white powder. GPC analysis of the resulting material indicated an M.sub.n of 8782 Da, a M.sub.w of 48367 Da, and a PDI of 5.51. This reaction is illustrated in Scheme 4.

##STR00017##

EXAMPLE 4

[0052] To a multineck round-bottomed flask containing a stir bar, DPO-CPD (1.72 g, 2.19 mmol) and DEBzOH-HEG from Example 2 (1.00 g, 2.30 mmol) were added via powder funnel, followed by PGMEA (30 mL). The reaction was stirred gently at room temperature. The flask was next equipped with a reflux condenser and an internal thermocouple probe attached to a self-regulating thermostat control for a heating mantle. Next, the dark maroon contents of the flask were warmed to an internal temperature of 105 C. and maintained at this temperature for 72 hours before cooling to 25 C. by removal of the heating element. The resulting maroon solution was precipitated from PGMEA using 500 mL isopropyl alcohol as an antisolvent. Filtration and drying of the precipitate under vacuum overnight yielded Polymer 2 as a white powder. GPC analysis indicated an M.sub.n of 10709 Da, an M.sub.w of 24442 Da, and a PDI of 2.28. This reaction is illustrated in Scheme 5.

##STR00018##

EXAMPLE 5

[0053] To an oven-dried single-necked 100 mL round-bottomed flask containing a stir bar, 3,5-diethynylphenol (DEP), tetrabutylammonium iodide (TBAI) and tetrahydrofuran (THF) are added via funnel, followed by triethylamine. The reaction is stirred gently at room temperature under a flowing blanket of nitrogen for 20 minutes before cooling in an ice water bath for 30 minutes. Epichlorohydrin is pre-dissolved in THF and is added dropwise into the reaction via syringe. The mixture is allowed to warm to room temperature as the ice bath melts, and is stirred overnight. The reaction is stopped by adding 500 mL of neutral aqueous buffer and extracting with two portions of 250 mL dichloromethane. The combined organic layers are washed with water and are then washed saturated aqueous sodium chloride, dried over sodium sulfate, and filtered. Concentration of the eluent and separation by neutral silica gel chromatography is expected to furnish 3,5-diethynylphenoxy glycidyl ether (DEP-GE).

EXAMPLE 6

[0054] Polyalkynyl-substituted aryl monomers of the invention are expected to be prepared according to the general procedure of Examples 1 or 2 except that DEBzOH and/or the hexa(ethylene glycol) are replaced by the reactants identified in Table 1.

TABLE-US-00001 TABLE 1 Monomer Reactant 1 Reactant 2 Procedure DEBzOH-DEG DEBzOH Diethylene glycol Example 2 DEBzOH-TEG DEBzOH Triethylene glycol Example 2 DEBzOH-Gly DEBzOH Glycerol Example 2 DEBzOH-EA DEBzOH Ethanolamine Example 2 DEBzOH-PA DEBzOH Propanolamine Example 2 DEBzOH-DEA DEBzOH Diethanolamine Example 2

EXAMPLE 7

[0055] Polyarylene oligomers of the invention are expected to be prepared according to the general procedure of Examples 3 or 4 except that the polyalkynyl-substituted aryl monomers having an adhesion-promoting moiety reported in Table 2 are reacted with DPO-CPD. In Table 2, where 2 or more monomers are used, the reported ratios are molar ratios, Abbreviations used in Table 6 and not defined elsewhere herein are: 1,3-DEB=1,3-di(ethynyl)benzene; 1,4-DEB=1,4-di(ethynyl)benzene; and TRIS=1,3,5-tris(phenylethynyl)-benzene.

TABLE-US-00002 TABLE 2 Polyalkynyl-substituted Aryl Polymer Monomer Procedure 3 DEP-GE Example 4 4 DEP-GE + 1,3-DEB (1.5:1) Example 4 5 DEBzOH-DEA Example 3 6 DEBzOH-DEA + TRIS (2:1) Example 4 7 DEBzOH-TEG + 1,4-DEB (1.7:1) Example 4 8 DEBzOH-GE + 1,3-DEB (1.2:1) Example 3 9 DEBzOH-HEG + TRIS (1:1) Example 4 10 DEBzOH-Gly Example 4 11 DEBzOH-PA + 1,3-DEB (2:1) Example 4

COMPARATIVE EXAMPLE

[0056] To a three neck round-bottomed flask containing a stir bar were added DPO-CPD (25 g, 31.9 mmol), DEBzOH (1.09 g, 6.4 mmol) and GBL (88 g). The reaction mixture was stirred gently at room temperature. The flask was next equipped with a reflux condenser and an internal thermocouple probe attached to a self-regulating thermostat control for a heating mantle. Next, the dark maroon contents of the flask were warmed to an internal temperature of 160 C. and maintained at this temperature for 4 hours before cooling to about 100 C. by removal of the heating element Next, TRIS (9.66 g, 25.5 mmol) was added slowly to the reaction. The resulting maroon solution was heated to 203 C. and stirred at this temperature for 47 hrs. GPC analysis of the reaction product (Comparative Polymer 1) indicated an M.sub.n of 8434 Da, an M.sub.w of 26395 Da, and a polydispersity of 3.13.

EXAMPLE 8

[0057] Crosslinkable formulations were prepared by combining Polymer 1 in PGMEA at 10% solids with an amount of PRIMENE MD cyclic diamine crosslinker. Sample 1 contained a 1:10 by weight mixture of crosslinker to Polymer 1 and Sample 2 contained a 1:50 mixture of crosslinker to Polymer 1. A Control Sample of only Polymer 1 in PGMEA was also prepared. A 1 g portion of each of Sample 1, Sample 2 and the Control Sample were added to separate 20 mL scintillation vials. The vials were warmed in a heating block to 100 C. without a cap, allowing the PGMEA to evaporate, and a thick film to form on the bottom of the vials. The temperature of the heating block was raised to 165 C., and the vials were kept at this external temperature for 1 hour. Next, 10 g of tetrahydrofuran (THF) was added to each vial. After contacting the film for 18 hours, an aliquot of the THF was diluted 2:98 for GPC sampling. For both Samples 1 and 2, the GPC analysis showed no polymer, indicating that solvent-resistant, crosslinked films had formed. Analysis of the Control Sample by GPC showed negligible change in molecular weight of Polymer 1, indicating that Polymer 1 was not crosslinked.

EXAMPLE 9

[0058] Films of the polymers reported in Table 3 were formed on both silicon and molybdenum-coated glass substrates by spin-coating compositions of the polymers in PGMEA (10% solids) at 1000 rpm for 90 seconds. Following deposition, the films were soft-baked at 110 C. for two minutes to remove most of the solvent prior to curing. The films were then cured under nitrogen in a belt furnace at 400 C. for one hour (belt speed was 25 mm per minute). Adhesion tests of the films were carried out using a standard cross-hatch method in which a lattice pattern was cut through the cured film using a cross-hatch cutter having six teeth spaced at 2.0 mm (Model P-A-T (PA2058) available from Paul N. Gardner Co., Inc.), exposing the substrate along the cut lines. The patterned area was briefly cleaned by exposure to pressurized air to remove any loose debris from the film surface. SCOTCH brand transparent tape (available from 3M) was firmly applied to the cross-hatch test area, and then quickly removed by peeling the tape off the film. The film was then examined under a microscope and adhesion was assessed on a scale from 0B to 5B using ASTM D3002 and D3359. In these adhesion tests, 0B indicates almost complete film loss and 5B indicates zero film loss. The results are reported in Table 3.

TABLE-US-00003 TABLE 3 Adhesion Rating Adhesion Rating Polymer Film On Silicon On Molybdenum Polymer 1 5B 5B Polymer 2 5B 5B Comparative 4B 4B Polymer 1

EXAMPLE 10

[0059] The general procedure of Example 9 was repeated on silicon wafers using Samples 3 and 4 and Control Sample 2. Sample 3 was prepared by combining Polymer 1 in PGMEA at 10% solids with an amount of PRIMENE MD cyclic diamine crosslinker in a weight ratio of 100:1 of Polymer 1 to crosslinker. Sample 4 was prepared by combining Polymer 1 in PGMEA at 10% solids with an amount of PRIMENE MD cyclic diamine crosslinker in a weight ratio of 100:10 of Polymer 1 to crosslinker. Control Sample 2 was prepared by combining Polymer 1 in PGMEA at 10% solids. Duplicate films of each of Samples 3 and 4 and Control Sample 2 were formed on separate silicon wafers according to the procedure of Example 9. A lattice pattern was cut through each of the cured films using a cross-hatch cutter according to Example 9, exposing the substrate along the cut lines. One set of films of each of the samples was evaluated according to the procedure of Example 9 and the adhesion results are reported in Table 4.

[0060] A second set of films of each of the samples was scored with a lattice pattern according to Example 9, but was then immersed in a conventional polymer remover solution comprising a mixture of N-methylpyrrolidone, an alkanolamine, and N-methylformamide in DPGME heated in a 70 C. water bath. After being immersed for 3 minutes, the samples were removed from the remover solution and rinsed with DI water for 10 seconds. Excess water was removed by gently patting the samples with paper towels followed by exposure to compressed air. Next, the samples were evaluated for adhesion according to the procedure of Example 9. These adhesion results (after exposure to a polymer remover) are reported in Table 4.

TABLE-US-00004 TABLE 4 Adhesion Rating Polymer Film Adhesion Rating After Exposure Control Sample 2 5B 1B Sample 3 5B 1B Sample 4 5B 5B

[0061] As can be seen from Table 4, the polymer film from Sample 4 shows excellent adhesion even after exposure to a conventional polymer remover solution.