Resins for underlayers

Abstract

Polymeric reaction products of certain substituted tetraarylmethane monomers are useful as underlayers in semiconductor manufacturing processes.

Claims

1. A polymeric reaction product comprising polymerized units of one or more tetraaryl monomers of formula (1) and one or more monomers chosen from formulae (2) and (3): ##STR00022## ##STR00023## wherein AG represents an activating group chosen from OR, NR.sub.2, and SR; Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 independently represent an aryl moiety; R is independently H, an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; a is an integer from 0 to 4; b, c, and d are independently integers from 0 to 5; R.sup.5 is selected from the group consisting of H, optionally substituted C.sub.1-60 aliphatic moiety, and optionally substituted C.sub.5-60 aryl moiety; Ar.sup.5 is an optionally substituted C.sub.5-60 aryl moiety, each R.sup.6 is independently chosen from H, optionally substituted C.sub.1-60 aliphatic moiety, and optionally substituted C.sub.5-60 aryl moiety, and X is OH, C.sub.1-2 alkoxy group or a halogen; wherein at least one of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 is an aryl moiety having 2 or more fused aromatic rings, and wherein none of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 are taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring.

2. The polymeric reaction product of claim 1 wherein AG is OR.

3. The polymeric reaction product of claim 1 wherein Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 are independently chosen from phenyl, biphenyl, naphthalenyl, anthracenyl, phenanthrenyl, pyrenyl, tetracenyl, triphenylenyl, tetraphenyl, benzo[f]tetraphenyl, benzo[m]tetraphenyl, benzo[k]tetraphenyl, pentacenyl, perylenyl, benzo[a]pyrenyl, benzo[e]pyrenyl, benzo[ghi]perylenyl, coronenyl, quinolonyl, 7,8-benzoquinolinyl, fluorenyl, chrysenyl, triphenylenyl, and 12H-dibenzo[b,h]fluorenyl.

4. A composition comprising the polymeric reaction product of claim 1, an organic solvent, and optionally one or more additives chosen from curing agents and surfactants.

5. The composition of claim 4 wherein the curing agent is an acid or a thermal acid generator.

6. A method of forming a patterned layer comprising disposing a layer of the composition of claim 4 on a substrate; removing organic solvent to form a polymeric underlayer; disposing a layer of a photoresist on the polymeric underlayer; exposing the photoresist layer to actinic radiation through a mask; developing the exposed photoresist layer to form a resist pattern; and transferring the pattern to the polymeric underlayer to expose portions of the substrate.

7. A tetraaryl methane monomer having the formula (1) ##STR00024## wherein AG represents an activating group chosen from OR, NR.sub.2, and SR; Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 independently represent an aryl moiety; R is independently H, an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; a is an integer from 0 to 4; and b, c, and d are independently integers from 0 to 5; wherein at least one of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 is an aryl moiety having 2 or more fused aromatic rings, and wherein none of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 are taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring; wherein when AG is OR, R is not a H atom, and wherein when AG is NR.sub.2 and one R is a H atom, the other R is not a C.sub.6 aryl moiety.

8. A tetraaryl monomer having the general formula (1-2): ##STR00025## AG represents an activating group chosen from OR, NR2, and SR; Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 independently represent an aryl moiety; R is independently H, an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; any 2 of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 may be taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring; a is an integer from 0 to 4; b is an integer from 0 to 5; and c and d are independently integers from 0 to 4; wherein when AG is NR.sub.2, the two groups are nor aryl moieties simultaneously.

9. A polymeric reaction product comprising polymerized units of one or more tetraaryl monomers of claim 8 and one or more monomers chosen from formulae (2) and (3): ##STR00026## wherein R.sup.5 is selected from the group consisting of H, optionally substituted C.sub.1-60 aliphatic moiety, and optionally substituted C.sub.5-60 aryl moiety; Ar.sup.5 is an optionally substituted C.sub.5-60 aryl moiety; each R.sup.6 is independently selected from the group consisting of H, optionally substituted C.sub.1-60 aliphatic moiety, and optionally substituted C.sub.5-60 aryl moiety; and X is OH, C.sub.1-2 alkoxy group or a halogen.

10. A composition comprising the polymeric reaction product of claim 9, an organic solvent, and optionally one or more additives chosen from curing agents and surfactants.

11. A method of forming a patterned layer comprising disposing a layer of the composition of claim 10 on a substrate; removing organic solvent to form a polymeric underlayer; disposing a layer of a photoresist on the polymeric underlayer; exposing the photoresist layer to actinic radiation through a mask; developing the exposed photoresist layer to form a resist pattern; and transferring the pattern to the polymeric underlayer to expose portions of the substrate.

12. A polymer comprising a repeat unit of formula (4) ##STR00027## wherein AG represents an activating group chosen from OR, NR.sub.2, and SR; Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 independently represent an aryl moiety; R is independently H, an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; any 2 of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 may be taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring; a is an integer from 0 to 4; and b, c, and d are independently integers from 0 to 5; wherein at least one of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 is an aryl moiety having 2 or more fused aromatic rings when none of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 are joined to form a 5 or 6-membered fused alicyclic ring; A is chosen from CH(R.sup.5), C(R.sup.6).sub.2Ar.sup.5C(R.sup.6).sub.2, or mixtures thereof; R.sup.5 is selected from the group consisting of H, optionally substituted C.sub.1-60 aliphatic moiety, and optionally substituted C.sub.5-60 aryl moiety; Ar.sup.5 is an optionally substituted C.sub.5-40 aryl moiety; Ar.sup.6 is an optionally substituted C.sub.5-60 aryl moiety; each R.sup.6 is independently chosen from H, optionally substituted C.sub.1-60 aliphatic moiety, and optionally substituted C.sub.5-60 aryl moiety; n and m each represent the number of repeat units in the polymer; n is an integer from 1 to 500; and m is an integer from 1 to 300.

13. The polymer of claim 12 wherein Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 are independently chosen from phenyl, biphenyl, naphthalenyl, anthracenyl, phenanthrenyl, pyrenyl, tetracenyl, triphenylenyl, tetraphenyl, benzo[f]tetraphenyl, benzo[m]tetraphenyl, benzo[k]tetraphenyl, pentacenyl, perylenyl, benzo[a]pyrenyl, benzo[e]pyrenyl, benzo[ghi]perylenyl, coronenyl, quinolonyl, 7,8-benzoquinolinyl, fluorenyl, chrysenyl, triphenylenyl, and 12H-dibenzo[b,h]fluorenyl.

14. The polymer of claim 12 wherein A is CH(R.sup.5).

15. The polymer of claim 12 wherein Ar.sup.5 is an optionally substituted C.sub.6-60 carbocyclic aryl moiety.

16. A composition comprising the polymer of claim 12, an organic solvent, and optionally one or more additives chosen from curing agents and surfactants.

17. A method of forming a patterned layer comprising disposing a layer of the composition of claim 16 on a substrate; removing organic solvent to form a polymeric underlayer; disposing a layer of a photoresist on the polymeric underlayer; exposing the photoresist layer to actinic radiation through a mask; developing the exposed photoresist layer to form a resist pattern; and transferring the pattern to the polymeric underlayer to expose portions of the substrate.

18. The method of claim 17 further comprising disposing a silicon-containing layer or a hardmask layer directly on the polymeric underlayer, and disposing the photoresist layer directly on the silicon-containing layer or hardmask layer.

19. A polymeric reaction product comprising polymerized units of one or more tetraaryl monomers of formula (1) ##STR00028## wherein AG represents an activating group chosen from OR, NR.sub.2, and SR; Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 independently represent an aryl moiety; R is independently H, an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently an optionally substituted C.sub.1-30 alkyl, an optionally substituted C.sub.2-30 alkenyl moiety, an optionally substituted C.sub.2-30 alkynyl moiety, an optionally substituted C.sub.7-30 aralkyl moiety, or an optionally substituted C.sub.6-20 aryl moiety; a is an integer from 0 to 4; and b, c, and d are independently integers from 0 to 5, wherein at least one of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 is an aryl moiety having 2 or more fused aromatic rings, and wherein none of Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 are taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring; and formed by heating the one or more tetraaryl monomers in the presence of an acid.

Description

EXAMPLE 1

(1) Under nitrogen atmosphere, a solution of 9-fluorenone (18.2 g, 100 mmol) in 150 mL of dry tetrahydrofuran (THF) was dropwise added at 0 C. to 100 mL of a 1M solution of phenylmagnesium bromide solution in THF. At the end of addition, the reaction mixture was stirred at room temperature for 16 hr. The reaction mixture was poured into 100 mL of saturated solution of ammonium chloride. The mixture was extracted twice with diethyl ether. The combined ether solution was dried over MgSO.sub.4 and the solvent was removed under reduced pressure to provide 19.5 g (76%) of intermediate (I1). .sup.1H NMR (CDCl.sub.3) : 7.72=7.73 (m, 2H), 7.27-7.57 (m, 11H). .sup.13C NMR (CDCl.sub.3) : 150.74, 143.5, 139.87, 135.02, 129.38, 128.75, 128.53, 127.51, 125.71, 125.12124.69, 120.619, 120.39.

(2) ##STR00019##

EXAMPLE 2

(3) To a solution of intermediate (I1) (7.6 g, 29.5 mmol) and phenol (2.7 g, 28.7 mmol) in 60 mL of 1,2-dichloroethane was added pTSA monohydrate (0.5 g, 2.6 mmol) and the mixture was stirred at 70 C. for 3 hr. The reaction mixture was transferred into a separation funnel and washed once with 50 mL of 0.5% aqueous solution of ammonium bicarbonate, followed by three washes with deionized water (50 mL each). The 1,2-dichloroethane was removed under reduced pressure to produce tetraaryl methane monomer (1-1a) (7.5 g, 85%). .sup.1H and .sup.13C NMR analysis showed that the product consisted of two structural isomers, which were not isolated. The product mixture was used in subsequent reactions.

EXAMPLE 3

(4) To a solution of intermediate (I1) (15 g, 58 mmol) and 2-naphthol (8.3 g, 57.57 mmol) in 100 mL of 1,2-dichloroethane was added pTSA monohydrate (0.8 g, 4.22 mmol) and the mixture was stirred at 70 C. for 4 hr. The reaction mixture was transferred into a separation funnel and washed once with 100 mL of 0.5% aqueous solution of ammonium bicarbonate, followed by two washes with deionized water (100 mL each). The 1,2-dichloroethane was removed under reduced pressure to produce tetraaryl methane monomer (1-1b) (20.3 g, 91%). .sup.1H and .sup.13C NMR analysis showed that the product consisted of structural isomers, which were not isolated. The product mixture was used in subsequent reactions.

EXAMPLE 4

(5) To a solution made of intermediate (I1) (8 g, 31.0 mmol) and pyrene-1-ol (6.5 g, 30 mmol) in 100 mL of 1,2-dichloroethane was added pTSA monohydrate (0.3 g, 1.57 mmol) and the mixture was stirred at 70 C. for 4 hr. The reaction mixture was cooled to room temperature and insoluble material was removed by filtration. The filtrate was washed once with 100 mL of 0.5% aqueous solution of ammonium bicarbonate, followed by two washes with deionized water (100 mL each). The 1,2-dichloroethane was removed under reduced pressure to produce tetraaryl methane monomer (1-1d) (6.9, 49%). .sup.1H and .sup.13C NMR analysis showed that the product consisted of structural isomers, which were not isolated. The product mixture was used in subsequent reactions.

EXAMPLE 5

(6) The procedure of Example 1 is repeated except that the phenylmagnesium bromide is replaced with -naphthylmagnesium bromide to provide intermediate (I2).

EXAMPLE 6

(7) The procedure of Example 1 is repeated except that the 9-fluorenone is replaced with anthraquinone and 200 mL of 1M phenylmagnesium bromide is used to provide intermediate (I3).

(8) ##STR00020##

EXAMPLE 7

(9) The procedure of Example 2 is repeated except that intermediate (I1) is replaced with triphenylmethanol (intermediate (I4)) to provide tetraaryl monomer (1a).

EXAMPLE 8

(10) The procedure of Example 3 is repeated except that intermediate (I1) is replaced with -(4-pyridyl)benzhydrol (intermediate (I5)) to provide tetraaryl monomer (1m).

(11) ##STR00021##

EXAMPLE 9

(12) The procedure of Example 3 is repeated except that the intermediate (I1) is replaced intermediate (I2) to provide tetraaryl monomer (1-1g).

EXAMPLE 10

(13) The procedure of Example 3 is repeated except that the intermediate (I1) is replaced intermediate (I3) and 105 mmol of 2-naphthol is used to provide tetraaryl monomer (1-2b).

EXAMPLE 11

(14) The procedure of Example 3 is repeated except that the intermediate (I1) is replaced intermediate (I3) and 60 mmol of pyrene-1-ol is used to provide tetraaryl monomer (1-2c).

EXAMPLE 12

(15) To a solution of tetraaryl monomer (1-1a) (5.0 g, 14.51 mmol) from Example 2 and paraformaldehyde (0.6 g, 19.8 mmol) in 15 mL propyleneglycol monomethylether acetate (PGMEA) was added pTSA monohydrate (0.15 g, 0.8 mmol). The reaction mixture was stirred under nitrogen atmosphere at 120 C. for 16 hr. The mixture was cooled to room temperature and poured slowly into methanol (200 mL) to precipitate polymer A. Polymer A was filtered off and washed with methanol. The resulting crude polymer was suspended in 30 mL of MeOH and stirred for 2 hr. at room temperature. The polymer was filtered and dried. The polymer was analyzed by GPC which showed M.sub.w=1940 and M.sub.w/M.sub.n=1.3.

EXAMPLE 13

(16) The procedure of Example 12 was repeated except that 13.0 g (33.8 mmol) of tetraaryl monomer (1-1b) from Example 3, 1.1 g (36.3 mmol) of paraformaldehyde, and 0.32 g (1.68 mmol) of pTSA in 45 mL of PGMEA were used to prepare polymer B. Polymer B was analyzed by GPC which showed M.sub.w=1400 and M.sub.w/M.sub.n=1.3.

EXAMPLE 14

(17) The procedure of Example 12 was repeated except that 8.0 g (16.85 mmol) of tetraaryl monomer (1-1d) from Example 4; 0.6 g (20.2 mmol) of paraformaldehyde, and 0.16 g (0.84 mmol) of pTSA in 25 mL of PGMEA were used to produce polymer C. Polymer C was analyzed by GPC which showed M.sub.w=2630 and M.sub.w/M.sub.n=1.8.

EXAMPLE 15

(18) The procedure of Example 14 was repeated except that 7.35 g (15.3 mmol) of tetraaryl monomer (1-1d) from Example 4; 2.4 g (15.36 mmol) of 2-napthaldehyde, and 0.5 g (5.2 mmol) of methanesulfonic acid in 30 mL of PGMEA were used to produce polymer D. Polymer D was analyzed by GPC which showed M.sub.w=1200 and M.sub.w/M.sub.n=1.3.

EXAMPLE 16

(19) The procedure of Example 12 is repeated except that paraformaldehyde is replaced with pyrenecarboxaldehyde and pTSA is replaced with methanesulfonic acid to produce polymer E.

EXAMPLE 17

(20) The procedure of Example 15 is repeated except that 2-napthaldehyde is replaced with 4-biphenylcarboxaldehyde to produce polymer F.

EXAMPLE 18

(21) The procedure of example 12 is repeated except that tetraaryl monomer (1-1a) is replaced with tetraaryl monomer (1a) to produce polymer G.

EXAMPLE 19

(22) The procedure of example 12 is repeated except that tetraaryl monomer (1-1a) is replaced with tetraaryl monomer (1m) to produce polymer H.

EXAMPLE 20

(23) The procedure of example 13 is repeated except that paraformaldehyde is replaced with phenanthrenecarboxaldehyde to provide polymer I.

EXAMPLE 21

(24) The procedure of Example 15 is repeated except that tetraaryl monomer (1-1d) is replaced with tetraaryl monomer (1-2c) to produce polymer J.

EXAMPLE 22

(25) The thermal stability of polymers of the invention were determined using thermal gravimetric analysis (TGA). Polymers A and B were individually formulated in propyleneglycol monomethylether acetate (PGMEA) at 10 wt % solids. Polymer C was formulated in cyclohexanone at 10% solids. Each solution was then filtered through 0.2 m poly(tetrafluoroethylene) (PTFE) syringe filter, coated on a silicon wafer at 1500 rpm and baked at 100 C. for 60 sec. to remove the solvent and further cured at 400 C. for 60 sec. The cured films were scraped off the wafers and analyzed by TGA. The results are reported in Table 1, and show that the present polymeric reaction products have good thermal stability.

(26) TABLE-US-00001 TABLE 1 Under Air Under Nitrogen Weight Temperature Temperature Weight Temperature Temperature loss at ( C.) at 5% ( C.) at 10% loss at ( C.) at 5% ( C.) at 10% Polymer 400 C. weight loss weight loss 400 C. weight loss weight loss A 6.8% 386 419 3.6% 423 475 B 3.6% 418 459 2.9% 426 467 C 3.6% 397 441 3.6% 416 452

EXAMPLE 23

(27) Polymers A and B were individually formulated in PGMEA at 10 wt % solids. Polymers C and D were formulated in cyclohexanone at 10% solid. Comparative polymers C1 (polycondensation product of 1-naphthol and formaldehyde, from Gun Ei Chemical, M.sub.w=6066, and M.sub.n=2362) and C2 (polycondensation product of 6,6-(9H-fluorene-9,9-diyl)bis(naphthalen-2-ol) and 1,4-bis(methoxymethyl)benzene, from Gun Ei Chemical) were formulated in PGMEA at 10 wt % solids. Each solution was then filtered through 0.2 m PTFE syringe filter, coated on a silicon wafer at 1500 rpm and baked at 100 C. for 60 sec. to remove the solvent and further cured at 400 C. for 60 sec. Each cured film was evaluated for etch selectivity using O.sub.2 and CF.sub.4 plasmas. The etch rate was calculated from the etch time and the difference in thickness of the film before and after etching. Etching tests were carried out using PLASMATHERM RIE790 from Plasma-Therm Co. The etching conditions are summarized in Table 2 and the etching results are reported in Table 3.

(28) TABLE-US-00002 TABLE 2 Gas O.sub.2 CF.sub.4 Flow (sscm) 60 50 Power (W) 700 500 Pressure (mTorr) 10 10

(29) TABLE-US-00003 TABLE 3 O.sub.2 etch CF.sub.4 etch Polymer (/sec.) (/sec.) A 30.3 3.0 B 28.6 4.1 C 26.0 2.0 D 27.1 5.1 C1 32.9 4.2 C2 34.2