SILICON-CONTAINING UNDERLAYERS

Abstract

Wet-strippable underlayer compositions comprising one or more silicon-containing polymers comprising a backbone comprising SiO linkages, one or more organic blend polymers, and a cure catalyst are provided. These compositions are useful in the manufacture of various electronic devices.

Claims

1. A composition comprising: one or more curable silicon-containing polymers comprising a backbone comprising SiO linkages; one or more organic blend polymers comprising as polymerized units one or more ethylenically unsaturated monomers having an acidic proton and having a pKa in water from 5 to 8, wherein the organic blend polymer comprises as polymerized units one or more monomers of formula (1) and one or more monomers of formula (2) ##STR00025## wherein Z is an organic residue having from 1 to 30 carbon atoms and an acidic proton having a pKa in water from 5 to 13; R.sup.20 is chosen from H, C.sub.1-10 alkyl, C.sub.1-10 haloalkyl, halo, C(O)R.sup.24 and Z; each of R.sup.21 and R.sup.22 are independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, halo, CN and Z; R.sup.24 is independently chosen from OR.sup.25 and N(R.sup.26).sub.2; R.sup.25 is chosen from H, and C.sub.1-20 alkyl; each R.sup.26 is independently chosen from H, C.sub.1-20 alkyl, and C.sub.6-20 aryl; wherein Z and R.sup.20 may be taken together to form a 5 to 7-membered unsaturated ring; ADG is an acid decomposable group; and R.sup.1 is independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, halo, and CN; and one or more cure catalysts.

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

3. The composition of claim 1 wherein the organic blend polymer further comprises as polymerized units one or more monomers of formula (9) ##STR00026## wherein R.sup.1 is independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, halo, and CN; and R.sup.2 is a monovalent organic residue having a lactone moiety.

4. The composition of claim 3 wherein the lactone moiety of R.sup.2 is a 5 to 7-membered ring or a substituted 5 to 7-membered ring.

5. The composition of claim 1 wherein the monomer of formula (2) has formula (2a) ##STR00027## wherein R.sup.5 is chosen from a C.sub.4-30 organic residue bound to the oxygen through a tertiary carbon or a C.sub.4-30 organic residue comprising an acetal functional group; and R.sup.1 is independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, halo, and CN.

6. The composition of claim 1 wherein the one or more silicon-containing polymers comprise as polymerized units one or more monomers chosen from formulae (3), (4), (5a), and (5b)
R.sup.3SiY.sub.3 (3)
SiY.sup.1.sub.4 (4)
R.sup.5.sub.2SiY.sup.2.sub.2 (5a)
R.sup.5.sub.3 SiY.sup.2 (5b) wherein each Y, Y.sup.1 and Y.sup.2 is independently a hydrolyzable moiety chosen from halo, C.sub.1-10 alkoxy, and OC(O)R.sup.4; R.sup.3 is C.sub.1-30 hydrocarbyl moiety or substituted C.sub.1-30 hydrocarbyl moiety; each R.sup.4 is chosen from H, OH, C.sub.1-10 alkyl, and C.sub.1-10 alkoxy; and each R.sup.5 is independently C.sub.1-30 hydrocarbyl moiety or substituted C.sub.1-30 hydrocarbyl moiety.

7. The composition of claim 6 wherein the one or more silicon-containing polymers comprise as polymerized units one or more units of formula (6) and optionally one or more units of formula (7) ##STR00028## wherein each R.sup.7 is independently chosen from C.sub.1-30 hydrocarbyl moiety, substituted C.sub.1-30 hydrocarbyl moiety, and OR.sup.8; each R.sup.8 is chosen from H, Si(R.sup.9).sub.xO(R.sup.10).sub.y, C.sub.1-30 hydrocarbyl moiety, and substituted C.sub.1-30 hydrocarbyl moiety; each R.sup.9 is independently C.sub.1-30 hydrocarbyl moiety or substituted C.sub.1-30 hydrocarbyl moiety; each R.sup.10 is independently H, C.sub.1-30 alkyl or C(O)C.sub.1-10 alkyl; each R.sup.11 is independently chosen from H, C.sub.1-10 alkyl, and C(O)C.sub.1-10 alkyl; n refers to the number of repeat units of formula (6) in the polymer and is an integer from 1 to 100; m refers to the number of repeat units of formula (7) in the polymer and is an integer from 0 to 50; x=0 to 3; y=0 to 3, and x+y=3.

8. The composition of claim 1 wherein the cure catalyst is a quaternary ammonium salt.

Description

SYNTHESIS EXAMPLE 1

Preparation of Silicon Polymer 1

[0044] Hydrochloric acid (6.15 g of 12.1N) in water (156 g) was added to a mixture of methyltrimethoxysilane (99.80 g), phenyltrimethoxysilane (50.41 g), vinyltrimethoxysilane (62.75 g) and tetraethyl orthosilicate (294 g) and 2-propanol (467 g) over 10 minutes. The reaction mixture was stirred at room temperature for 1 hr., heated to reflux for 24 hr. and cooled to room temperature. The solution was diluted with PGEE (800 g) and low boiling reaction mixture components were removed under reduced pressure. The resulting solution was diluted with PGEE to afford a final 10 wt % solution of Silicon Polymer 1 (M.sub.w=9000 Da).

SYNTHESIS EXAMPLE 2

Preparation of Silicon Polymer 2

[0045] Acetic acid (35.5 g) in water (160 g) was added to a mixture of methyltrimethoxysilane (99.8 g), phenyltrimethoxysilane (50.4 g), vinyltrimethoxysilane (62.8 g) and tetraethyl orthosilicate (294 g) and PGMEA (467 g) over 10 min. The reaction mixture was stirred at room temperature for 1 hr., heated to 85 C. for 6 hr. and then cooled to room temperature. Low boiling reaction mixture components were removed under reduced pressure and the resulting solution was diluted with PGMEA to afford a final solution of Silicon Polymer 2 (ca. 10-12 wt %) (M.sub.w=4000 Da).

SYNTHESIS EXAMPLE 3

Preparation of Silicon Polymer 3

[0046] H Hydrochloric acid (0.265 g of 12.1N) in water (29.4 g) was added to a mixture of vinyltrimethoxysilane (4.75 g), phenyltrimethoxysilane (12.7 g), bis(triethoxysilyl)ethylene (83.5 g) and 2-propanol (160 g) over 10 min. The reaction mixture was stirred at room temperature for 1 hr., heated to reflux for 18 hr. and then cooled to room temperature. The solution was diluted with PGEE (300 g) and low boiling reaction mixture components were removed under reduced pressure. The resulting solution of Silicon Polymer 3 was diluted with PGEE to afford a final concentration of 10 wt % (M.sub.w=28000 Da).

SYNTHESIS EXAMPLE 4

Preparation of Silicon Polymer 4

[0047] Hydrochloric acid (6.15 g of 12.1N) in water (225 g) was added to a mixture of 3-(3-(triethoxysilyl)propyl)dihydrofuran-2,5-dione (223 g), phenyltrimethoxysilane (50.41 g), vinyltrimethoxysilane (62.75 g) and tetraethyl orthosilicate (294 g) and 2-propanol (467 g) over 10 min. The reaction mixture was stirred at room temperature for 1 hr., heated to reflux for 24 hr. and then cooled to room temperature. The solution was diluted with PGEE (800 g) and low boiling reaction mixture components were removed under reduced pressure. The resulting solution was diluted with PGEE to afford a final 10 wt % solution of Silicon Polymer 4 (M.sub.w=3900 Da).

SYNTHESIS EXAMPLE 5

Preparation of Silicon Polymer 5

[0048] Hydrochloric acid (0.615 g of 12.1N) in water (15.6 g) was added to a mixture of (triethoxysilyl)methyl acetate (17.3 g), phenyltrimethoxysilane (5.04 g), vinyltrimethoxysilane (6.28 g), tetraethyl orthosilicate (29.4 g) and 2-propanol (46.7 g) over 10 min. The reaction mixture was stirred at room temperature for 1 hr., heated to reflux for 24 hr. and cooled to room temperature. The solution was diluted with PGEE (80 g) and low boiling reaction mixture components were removed under reduced pressure. The resulting solution was diluted with PGEE to afford a final 10 wt % solution of Silicon Polymer 5 (M.sub.w=8500 Da).

SYNTHESIS EXAMPLE 6

Preparation of Silicon Polymer 6

[0049] Hydrochloric acid (0.615 g of 12.1N) in water (15.6 g) was added to a mixture of (triethoxysilyl)methyl acetate (17.3 g), phenyltrimethoxysilane (5.04 g), vinyltrimethoxysilane (6.28 g) tetraethyl orthosilicate (29.4 g), propoxylated pentaerythritol (3.60 g) and 2-propanol (46.7 g) over 10 min. The reaction mixture was stirred at room temperature for 1 hr., heated to reflux for 24 hr. and cooled to room temperature. The solution was diluted with PGEE (80 g) and low boiling reaction mixture components were removed under reduced pressure. The resulting solution was diluted with PGEE to afford a final 10 wt % solution of Silicon Polymer 6 (M.sub.w=4100 Da).

SYNTHESIS EXAMPLE 7

Preparation of Silicon Polymer 7

[0050] Hydrochloric acid (0.615 g of 12.1N) in water (15.6 g) was added to a mixture of tert-butyl 2-methyl-3-(triisopropoxysilyl)-propanoate (14.7 g), (4-(3-(diethoxy(methyl)silyl)propoxy)-2-hydroxyphenyl)(phenyl)methanone (10.9 g), tetraethyl orthosilicate (29.4 g), and 2-propanol (46.7 g) over 10 min. The reaction mixture was stirred at room temperature for 1 hr., heated to reflux for 24 hr. and cooled to room temperature. The solution was diluted with PGEE (80 g) and low boiling reaction mixture components were removed under reduced pressure. The resulting solution was diluted with PGEE to afford a final 10 wt % solution of Silicon Polymer 7 (M.sub.w=4600 Da).

SYNTHESIS EXAMPLE 8

Preparation of Organic Polymer 1

[0051] A solution of 2-hydroxyethyl methacrylate (HEMA), (3.34 g) gamma butyrolactone (GBLMA), (4.37 g) tert-butylmethacrylate (tBMA), (3.65 g) and methacrylic acid (2.21 g) dissolved in 1,3-dioxolane (11.5 g) and a solution of V-65 initiator (2.55 g) dissolved in 2:1 v/v tetrahydrofurane/acetonitrile (2.55 g) were both added dropwise over 2 hr. to 3-dioxolane (26.7 g) at 75 C. under a nitrogen blanket. After addition, the reaction solution was held at 75 C. for an additional 2 hr., cooled to room temperature, diluted with 15 g THF and isolated by drop-wise addition into 500 mL of stirred di-diopropylether. The precipitated polymer was collected by vacuum filtration and vacuum oven dried for 24 hr. to afford Organic Polymer 1 as a white solid (10.2 g, 75%). M.sub.w was determined to be 4000 Da.

SYNTHESIS EXAMPLES 9-24

[0052] Organic Polymers 2 to 4 and 6 to 17, reported in Table 2 below, were synthesized according to Synthesis Example 8 above using the monomers listed in Table 1 below. Organic Polymers 2 to 4 and 6 to 17 were isolated in 50-99% yield and had a M.sub.w between 3500-3800 Da. Organic Polymer 5 was a commercially available polymer from DuPont.

TABLE-US-00001 TABLE 1 [00009] Monomer 1 [00010] Monomer 2 [00011] Monomer 3 [00012] Monomer 4 [00013] Monomer 5 [00014] Monomer 6 [00015] Monomer 7 [00016] Monomer 8 [00017] Monomer 9 [00018] Monomer 10 [00019] Monomer 11 [00020] Monomer 12 [00021] Monomer 13 [00022] Monomer 14 [00023] Monomer 15 [00024] Monomer 16

TABLE-US-00002 TABLE 2 Organic Monomer A Monomer B Monomer C Monomer D Example Polymer (mol %) (mol %) (mol %) (mol %) 9 2 Monomer 5 Monomer 7 (40) (60) 10 3 Monomer 5 (100) 11 4 Monomer 1 Monomer 5 (40) (60) 12 5 Monomer 6 (100) 13 6 Monomer 5 Monomer 7 (60) (40) 14 7 Monomer 5 Monomer 7 Monomer 1 (60) (20) (20) 15 8 Monomer 5 Monomer 7 (80) (20) 16 9 Monomer 5 Monomer 7 Monomer 4 (40) (50) (10) 17 10 Monomer 8 Monomer 7 Monomer 4 (35) (55) (10) 18 11 Monomer 3 Monomer 2 Monomer 1 Monomer 4 (40) (25) (25) (10) 19 12 Monomer 2 Monomer 1 Monomer 4 (25) (250 (50) 20 13 Monomer 9 Monomer 2 Monomer 10 Monomer 4 (20) (30) (20) (30) 21 14 Monomer 11 Monomer 12 Monomer 13 Monomer 4 (27) (33) (25) (15) 22 15 Monomer 2 Monomer 14 Monomer 10 Monomer 4 (22) (33) (25) (20) 23 16 Monomer 14 Monomer 2 Monomer 15 Monomer 4 (30) (40) (20) (10) 24 17 Monomer 16 Monomer 2 Monomer 15 (40) (40) (20)

Formulation Examples

[0053] Formulations 1-30 and Comparative Formulations C1-C6 were prepared by combining the amount of each of the following components described in Table 3. The Silicon Polymer Solutions, Organic Polymer Solutions, and catalysts used are described in Table 4. In Table 3, Organic Polymer/OPS refers to the Organic Polymers of the invention from Examples 8 to 24 and to the particular Organic Polymer Solutions (OPS) from Table 4 made using the specified Organic Polymer. Where no OPS is indicated used, the specified weight is the weight of dry Organic Polymer added. Where an OPS is indicated, the weight is the weight of the OPS added.

TABLE-US-00003 TABLE 3 Silicon Polymer Organic Formu- Solution Polymer/OPS Catalyst Solvent lation (g) (g) (g) (g) 1 B (1.26) Polymer 2 3 (0.284) PGMEA (14.8)/ (0.14) EL (0.60) 2 B (1.76) Polymer 2 3 (0.284) PGMEA (14.3)/ (0.47) EL (0.60) 3 B (1.26) Polymer 3/ 3 (0.284) PGMEA (14.8)/ (0.14) EL (0.60) 4 B (1.76) Polymer 3 3 (0.284) PGMEA (14.3)/ (0.09) EL (0.60) 5 B (1.26) Polymer 4 3 (0.284) PGMEA (14.8)/ (0.14) EL (0.60) 6 B (1.76) Polymer 4 3 (0.284) PGMEA (14.3)/ (0.09) EL (0.60) 7 C (1.27) Polymer 5/ 3 (0.288) PGMEA (13.4)/ OPS2 (1.44) EL (0.60) 8 C (2.47) Polymer 6/ 3 (0.400) PGMEA (16.3)/ OPS2 (0.48) EL (3.29) 9 C (2.47) Polymer 7/ 3 (0.400) PGMEA (16.3)/ OPS2 ( ).48) EL (3.29) 10 C (2.47) Polymer 8/ 3 (0.400) PGMEA (16.3)/ OPS2 (0.48) EL (3.29) 11 C (1.78) Polymer 9/ 3 (0.288) PGMEA (12.1)/ OPS1 (0.43) EL (2.37) 12 C (1.28) Polymer 9/ 3 (0.288) PGMEA (12.1)/ OPS1 (0.719) EL (2.37) 13 C (1.78) Polymer 10/ 3 (0.288) PGMEA (12.1)/ OPS1 (0.43) EL (2.37) 14 C (1.28) Polymer 10/ 3 (0.288) PGMEA (12.1)/ OPS1 (0.72) EL (2.37) 15 D (8.31) Polymer 1/ 4 (0.320) PGEE (32.0)/ OPS6 (3.56) HBM (40.8) 16 D (8.31) Polymer 10/ 4 (0.320) PGEE (32.0)/ OPS6 (3.56) HBM (40.8) 17 E (1.66) Polymer 1/ 1 (0.640) PGEE (32.0)/ OPS6 (0.71) HBM (8.23) 18 A (19.8) Polymer 1/ 4 (1.07) PGEE (67.9)/ OPS4 (19.8) EL (79.0) 19 .sup.A (15.80 Polymer 1/ 4 (1.07) PGEE (71.4)/ OPS4 (23.8) EL (75.4) 20 A (13.9) Polymer 1/ 4 (1.07) PGEE (3.2)/ OPS4 (25.7) EL (73.7) 21 .sup.F (2.88) Polymer 12/ 1 (0.914) PGEE (4.54)/ OPS6 (1.02) EL (7.9) 22 .sup.F (2.38) Polymer 1/ 1 (0.914) PGEE (4.54)/ OPS6 (1.02) EL (7.9) 23 G (2.38) Polymer 1/ 1 (0.914) PGEE (4.54)/ OPS6 (1.02) EL (7.9) 24 H (2.88) Polymer 1/ 1 (0.777) PGEE (4.33)/ OPS6 (0.87) HBM (8.85) 25 A (1.44) Polymer 13/ 1 (0.777) PGEE (5.62)/ OPS6 (1.44) HBM (7.55) 26 A (1.44) Polymer 14/ 1 (0.777) PGEE (5.62)/ OPS6 (1.44) HBM (7.55) 27 A (1.44) Polymer 15/ 1 (0.777) PGEE (5.62)/ OPS6 (1.44) HBM (7.55) 28 A (1.44) Polymer 16/ 1 (0.777) PGEE (5.62)/ OPS6 (1.44) HBM (7.55) 29 A (1.44) Polymer 17/ 1 (0.777) PGEE (5.62)/ OPS6 (1.44) HBM (7.55) 30 I (2.88) Polymer 1/ 1 (0.777) PGEE (4.33)/ OPS6 (2.02) HBM (8.85) C1 A (2.38) 1 (0.64) PGEE (5.66)/ EL (8.24) C2 E (2.38) 1 (0.64) PGEE (5.02)/ HBM (8.87) C3 .sup.F (2.88) 1 (0.78) PGEE (4.33)/ EL (8.84) C4 G (2.88) 1 (0.78) PGEE (4.33)/ HBM (8.85) C5 H (2.88) 1 (0.78) PGEE (4.33)/ HBM (8.85) C6 I (2.88) 1 (0.78) PGEE (4.33)/ HBM (8.85)

TABLE-US-00004 TABLE 4 Component Description Silicon Polymer Silicon Polymer 1 (10 wt %) in PGEE Solution A Silicon Polymer Silicon Polymer 2 (11.3 wt %) in PGMEA Solution B Silicon Polymer Silicon Polymer 2 (10.8 wt %) in PGMEA Solution C Silicon Polymer Silicon Polymer 1 (11.3 wt %) in PGEE Solution D Silicon Polymer Silicon Polymer 3 (10 wt %) in PGEE Solution E Silicon Polymer Silicon Polymer 4 (10 wt %) in PGEE Solution F Silicon Polymer Silicon Polymer 5 (10 wt %) in PGEE Solution G Silicon Polymer Silicon Polymer 6 (10 wt %) in PGEE Solution H Silicon Polymer Silicon Polymer 7 (10 wt %) in PGEE Solution I OPS1 20 wt % of any of Organic Polymers 1-17 in PGMEA OPS2 10 wt % of any of Organic Polymers 1-17 in PGMEA OPS3 5 wt % of any of Organic Polymers 1-17 in PGMEA OPS4 10 wt % of any of Organic Polymers 1-17 in EL OPS5 10 wt % of any of Organic Polymers 1-17 in HBM OPS6 10 wt % of any of Organic Polymers 1-17 in PGEE Catalyst 1 0.1 wt % of tetrabutylammonium chloride in PGEE Catalyst 2 0.1 wt % of tetramethylammonium chloride in PGMEA Catalyst 3 0.1 wt % of tetramethylammonium chloride in EL Catalyst 4 1 wt % of tetrabutylammonium chloride in PGEE

[0054] Wet Strippability. Formulation samples tested were filtered through 0.2 m polytetrafluoroethylene syringe and were spin-coated on bare 200 mm silicon wafers at 1500 rpm and baked at 240 C. for 60 sec. using an ACT-8 Clean Track (Tokyo Electron Co.). Film thickness after baking of each coated film was measured with an OptiProbe instrument from Therma-wave Co. The coated sample was then evaluated for SC-1 wet strippability using a mixture of 30% NH.sub.4OH/30% H.sub.2O.sub.2/water in a w/w/w ratio of 1/1/5, 1/5/40, or 1/1/40. The SC-1 mixture was heated to 70 C. Coupons of each coated wafer were immersed into the stripping solution for 5 min. The coupons were removed from the SC-1 mixture and rinsed with deionized water. The film thickness loss for each sample was calculated as the difference in film thickness before and after contact with the SC-1 stripping mixture. A separate film prepared as described above is optionally tested for SC-1 strippability after etching. Etching was performed for 60 sec. using RIE790 from Plasma-Therm Co. with oxygen gas, 25 sscm flow, 180 W of power, and 6 mTorr of pressure.

[0055] The data for a stripping mixture of 30% NH.sub.4OH/30% H.sub.2O.sub.2/water in a 1/1/5 w/w/w ratio are reported in Table 5 versus Comparative Formulation C1, in Table 6 for a 1/5/40 w/w/w ratio versus Comparative Formulation C1, in Table 7 for a 1/5/40 w/w/w ratio versus Comparative Formulation C2, and in Table 8 for a 1/1/40 w/w/w ration versus Comparative Formulations C1 and C3-C6. Data labeled as No Etch were calculated as a percentage by taking the difference in film thickness between the coated wafer and the film thickness after exposure to the SC-1 stripping mixture. Data labeled as After Etch were calculated as a percentage by taking the difference in film thickness between the coated wafer after exposure to oxygen etch and the film thickness after the same wafer was exposed to the SC-1 stripping mixture.

[0056] In Tables 5 to 8, the stripping data for the respective Comparative Formulation were normalized to 1.00, and designated with . Inventive examples that outperformed the Comparative Formulation by <2 times are designated with .square-solid.; inventive examples that outperformed the Comparative Formulation by 2 to 10 times are designated with ; inventive examples that outperformed the Comparative Formulation by 10 to 30 times are designated with ; and inventive examples that outperformed the Comparative Formulation by over 30 times are designated with .

TABLE-US-00005 TABLE 5 SC-1 1/1/5 w/w/w Formulation No Etch After Etch C1 1 2 3 4 5 6 7 8 9 10 11 12 13 14

TABLE-US-00006 TABLE 6 SC-1 1/5/40 w/w/w Formulation No Etch C1 15 16

TABLE-US-00007 TABLE 7 SC-1 1/5/40 w/w/w Formulation No Etch C2 17

TABLE-US-00008 TABLE 8 SC-1 1/1/40 w/w/w Formulation No Etch After Etch C1 C3 C4 C5 C6 20 .sup.1 .sup.1 21 .sup.1 .sup.1 22 .sup.1 .sup.1 24 .sup.2, .sup.1 .sup.2 25 .sup.2, .sup.1 .sup.2 27 .square-solid..sup.3, .sup.1 .sup.3 29 .sup.4 .sup.4 30 .sup.1 .sup.1 31 .sup.1 .sup.1 32 .sup.1 .sup.1 33 .sup.1 .sup.1 34 .square-solid..sup.1 .sup.1 36 .sup.5 .sup.5 .sup.1Relative to C1. .sup.2Relative to C3. .sup.3Relative to C4. .sup.4Relative to C5. .sup.5Relative to C6.

[0057] The data in Tables 5-8 clearly show that the formulations of the invention improve the wet strippability of silicon-containing materials.