Aromatic resins for underlayers

Abstract

Polyarylene resins and compositions containing them are useful as underlayers in semiconductor manufacturing processes.

Claims

1. A polyarylene resin comprising as polymerized units one or more first monomers of formula (1) ##STR00032## wherein Ar is a C.sub.5-60-aryl moiety; each Ar.sup.3 and Ar.sup.4 is independently a C.sub.5-30-aryl moiety; each R.sup.1 is independently chosen from —OH and —C(═O)OR.sup.3; each R.sup.2 is independently chosen from C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, C.sub.5-30-aryl, CN, and halo; R.sup.3=H or M; M=an alkali metal ion, an alkaline earth metal ion, or an ammonium ion; each a3 is independently 0 to 3; each a4 is independently 0 to 3; b1=1 to 4; b2=0 to 4; each c3 is independently 0 to 3; each c4 is independently 0 to 3; a3+a4=1 to 6; and b1+b2=2 to 6; and one or more second monomers comprising two or more cyclopentadienone moieties.

2. The polyarylene resin of claim 1, wherein the first monomer has the formula ##STR00033## wherein Ar.sup.1 is a C.sub.5-30 aryl moiety; a1=0 to 3; and c1=0 to 3.

3. The polyarylene resin of claim 1 wherein a3+a4=2 to 4.

4. The polyarylene resin of claim 1 wherein b1+b2=2 to 4.

5. The polyarylene resin of claim 1 further comprising as polymerized units one or more third monomers of formula (13) ##STR00034## wherein Ar.sup.7 is a C.sub.5-30-aromatic moiety; each Y.sup.2 is independently a chemical bond or a divalent linking group chosen from —O—, —S—, —S(═O)—, —S(═O).sub.2—, —C(═O)—, —(C(R.sup.9).sub.2).sub.z—, C.sub.6-30 aryl, and —(C(R.sup.9).sub.2).sub.z1—(C.sub.6-30 aryl)-(C(R.sup.9).sub.2).sub.z2 ; each R is independently chosen from H or a C.sub.5-30-aryl moiety; each R.sup.15 is independently chosen from C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, C.sub.1-4-alkoxy, optionally substituted C.sub.7-14-aralkyl, and optionally substituted C.sub.6-30-aryl; b4=1 or 2;f=0 to 4; z is 1 to 10; z1 is 0 to 10; z2 is 0 to 10; and z2 is 0 to 10; and z1+z2=1 to 10.

6. The polyarylene resin of claim 5 wherein f=0.

7. The polyarylene resin of claim 1 wherein the one or more second monomers are chosen from one or more monomers of formula (9) ##STR00035## wherein each R.sup.10 is independently chosen from H, C.sub.1-6-alkyl, or optionally substituted C.sub.5-30-aryl; and Ar.sup.5 is an aromatic moiety having from 5 to 60 carbon atoms.

8. A composition comprising the polyarylene resin of claim 1 and one or more organic solvents.

9. A method of forming a patterned layer comprising: (a) coating on a substrate a layer of the composition of claim 8 (b) removing organic solvent to form a polyarylene resin layer; (c) coating a layer of a photoresist on the polyarylene resin layer; (d) exposing the photoresist layer to actinic radiation through a mask; (e) developing the exposed photoresist layer to form a resist pattern; and (f) transferring the pattern to the polyarylene resin layer to expose portions of the substrate.

10. The method of claim 9 further comprising the steps of patterning the substrate; and then removing the patterned polyarylene resin layer.

11. The method of claim 9 further comprising the step of coating a silicon-containing layer over the polyarylene resin layer before step (c).

12. The method of claim 11 further comprising the step of transferring the pattern to the silicon-containing layer after step (c) and before step (d).

Description

EXAMPLE 1

Preparation of 3,5-Bis(phenylethynyl)phenol

(1) 3,5-Dibromophenol acetate (44.10 g) and cuprous iodide (2.88 g) were added into a round bottom flask under nitrogen. To this solution, 1,4-dioxane (80 mL) and triethylamine (45.50 g) were added. The mixture was purged with nitrogen for 1 hr., and bis(triphenylphosphine)palladium(II) chloride (5.25 g) was added. The mixture was then heated to 60° C., and phenylacetylene (45.90 g) was added dropwise to the reaction within 1 hr. After the addition, the reaction was heated to 70° C. and stirred overnight. The reaction mixture was cooled to room temperature, and the solvent was removed by rotary evaporation. A mixture of ethyl acetate and heptane (200 mL, 1:3 v/v) was added to the residue mixture, and the mixture was filtered through silica gel, and washed with this solvent until thin layer chromatography showed no product on silica gel. The filtrates were combined and concentrated, and 150 mL heptane was added. The mixture was stirred for 1 hr., filtered and dried to obtain 3,5-bis(phenylethynyl)phenol acetate as a yellow solid (40.66 g, 80.58% yield). NMR (600 MHz, CDCl.sub.3): δ 7.58 (t, J=1.4 Hz, 1H), 7.53-7.52 (m, 4H), 7.37-7.35 (m, 6H), 7.24 (d, J=1.4 Hz, 2H), 2.32 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3): δ 169.10, 150.51, 132.26, 131.84, 128.79, 128.55, 125.00, 124.72, 122.89, 90.87, 87.84, 21.22

(2) This obtained solid (3,5-bis(phenylethynyl)phenol acetate) was dissolved in tetrahydrofuran (THF) (140 mL) under nitrogen. Lithium hydroxy monohydrate (18.88 g) and 32 mL of water were added, and the mixture was stirred at 60° C. for 3 hours. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of aqueous layer was 4 to 5. The organic phase was separated and aqueous phase was extracted with ethyl acetate. The organic layers were combined, and washed with water for three times. The solvent was removed under vacuum. A mixture of ethyl acetate and heptane (80 mL, 1:3 v/v) was added to the organic layer. The mixture was filtered through silica gel, and washed with this solvent until thin layer chromatography showed no product on silica gel. The solvent was removed under vacuum, and heptane (150 mL) was added. The mixture was stirred for 1 hour, filtered and dried under vacuum to obtain the product, 3,5-bis(phenylethynyl)phenol (BPEP), as a yellow solid (30.54 g) in 85.84% yield. .sup.1H NMR (600 MHz, CDCl.sub.3): δ 7.55-7.53 (m, 4H), 7.37-7.33 (m, 7H), 6.98 (s, 2H), 4.97 (s, 1H); .sup.13C NMR (151 MHz, CDCl.sub.3): δ 155.40, 131.92, 128.76, 128.63, 127.95, 125.04, 123.12, 118.66, 90.24, 88.47. The overall reaction is shown in Scheme 2.

(3) ##STR00016##

EXAMPLE 2

Preparation of 1,3,5-tris(4-acetoxyphenylethynyl)benzene

(4) 1,3,5-Tribromo-benzene (2.36 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 21.03 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70° C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in 5 mL degassed 1,4-dioxane, and the solution was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction was stirred for 24 hr. at 70° C. under nitrogen. After reaction was completed, the mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was dissolved in ethyl acetate/heptane (v/v 1:3) solvent mixture and filtered through a silica plug. After filtration, the solvents were removed to yield a light yellow solid 3.50 g (84.5% yield). This reaction is illustrated in Scheme 3.

(5) ##STR00017##

EXAMPLE 3

Preparation of Polymer 1

(6) Diphenylene oxide bis(triphenyl-cyclopentadienone) (DPO-CPD) (3.52 g) and 1,3,5-tris(4-acetoxyphenylethynyl)benzene (2.74 g) from Example 2 were dissolved in 14.60 g of GBL. The reaction was heated at 200° C. for 23 hr. The reaction mixture was cooled to room temperature, and slowly added to warm water. The precipitated polymer was collected by filtration and then dried in vacuum oven at 65 to 70° C. for 2 days. Polymer 1 was obtained as a brown solid (5.60 g) in 97% yield. GPC: M.sub.w=8156, PDI=2.0.

EXAMPLE 4

Preparation of Polymer 2

(7) Polymer 1 (5.60 g) from Example 3 was dissolved in 50 mL THF at room temperature. Lithium hydroxide hydrate (0.94 g) in 15 mL water was then added to the mixture. The reaction mixture was heated to 60° C. overnight. After the reaction was completed, the reaction mixture was neutralized with HCl, and diluted with water. The precipitated polymer was collected by filtration, washed with hot water and then dried in vacuum oven at 65 to 70° C. for 2 days. Polymer 2 was obtained as a brown solid 4.80 g (95% yield). GPC: M.sub.w=9987, PDI=2.1. This reaction is shown in Scheme 4.

(8) ##STR00018##

EXAMPLE 5

Preparation of 1,3-Bis(4-acetoxyphenylethynyl)benzene (BisAPEB)

(9) 4-Bromophenyl acetate (26.88 g), cuprous iodide (0.95 g) and triethylamine (15.18 g) were added to 94.85 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (1.75 g) was added to the reaction mixture, and the mixture was heated to 70° C. 1,3-Diethynylbenzene (6.31 g) was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction was stirred for 24 hr. at 70° C. under nitrogen. After reaction was completed, the mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was dissolved in ethyl acetate/heptane (v/v 1:5) solvent mixture and filtered through a silica plug. After filtration, the solvents were removed to yield 3.50 g (84.5% yield) of BisAPEB as a light yellow solid.

(10) ##STR00019##

EXAMPLE 6

Preparation of Polymer 3

(11) The general procedure of Example 3 is repeated except that the 1,3,5-tris(4-acetoxyphenylethynyl)benzene from Example 2 is replaced with BisAPEB from Example 5 and is expected to yield Polymer 3.

EXAMPLE 7

Preparation of Polymer 4

(12) The general procedure of Example 4 is repeated except that Polymer 3 is used instead of Polymer 1, and is expected to yield Polymer 4.

EXAMPLE 8

(13) The general procedure of Example 3 is repeated, except that 1,3,5-tris(4-acetoxyphenylethynyl)benzene is replaced with one of the monomers in Table 1 and is expected to provide the Polymers indicated in Table 1, where *=the point of attachment to the carbon-carbon triple bond in the structure shown in the Structure column.

(14) TABLE-US-00001 TABLE 1 Monomer No. Structure Ar Polymer 8-1 0 5 8-2 6 8-3 7 8-4 8 8-5 9 8-6 0 10

EXAMPLE 9

Preparation of Polymer 11

(15) The general procedure of Example 3 is repeated except that a mixture of 1,3,5-tris(4-acetoxyphenylethynyl)benzene from Example 2 and BPEP from Example 1 are reacted with DPO-CPD and expected to provide Polymer 11.

EXAMPLE 10

Preparation of 1,3,5-Tris-((4-fluorophenyl)ethynyl)benzene (TrisFPEB)

(16) 1,3,5-Tribromobenzene (15.0 g) was added to 40.0 g of 1,4-dioxane at room temperature to yield a clear solution. Triethylamine (14.5 g) and cuprous iodide (0.91 g) were added to the reaction mixture. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (1.00 g) was added to the reaction mixture. Next, 22.9 g of 4-fluorophenyl acetylene was slowly added to reaction mixture via an addition funnel. After completion of addition, the reaction was stirred for 24 hr. at 55° C. under nitrogen. The mixture was filtered and solvents were evaporated. The residue was dissolved in heptanes and filtered through a silica plug. After filtration, the solvents were removed to yield TrisFPEB as a light yellow solid (8.0 g) in 39% yield.

EXAMPLE 11

Preparation of Polymer 12

(17) DPO-CPD (6.00 g) and TrisFPEB (3.98 g) from Example 10 were dissolved in 21.2 g of GBL. The reaction was heated at 200° C. for 36 hr. The mixture was cooled to room temperature and then diluted with 5 g of GBL. The reaction mixture was slowly added to warm water. The precipitated polymer (Polymer 12) was collected by filtration and then dried in vacuum oven at 65 to 70° C. for 2 days to provide Polymer 11 9.0 g of a brown solid in 90% yield. GPC: M.sub.w=5014, PDI=1.78.