SILICON-CONTAINING UNDERLAYERS

Abstract

Methods of manufacturing electronic devices employing wet-strippable underlayer compositions comprising a condensate and/or hydrolyzate of a polymer comprising as polymerized units one or more first unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to the polymer backbone, and one or more condensable silicon monomers are provided.

Claims

1. A composition comprising: (a) one or more solvents; (b) a condensate and/or hydrolyzate of (i) one or more condensed silicon-containing polymers comprising as polymerized units one or more first unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to the polymer backbone, the one or more first unsaturated monomers having the formula (1) ##STR00035## wherein L is a single bond or a divalent linking group; each R.sup.1 is independently chosen from H, C.sub.1-10-alkyl, C-alkenyl, C.sub.5-20-aryl, and C.sub.6-20-aralkyl; each of R.sup.2 and R.sup.3 are independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, halogen, C.sub.5-20-aryl, C.sub.6-20 aralkyl, and CN; R.sup.4 is chosen from H, C.sub.1-10 alkyl, C.sub.1-10 haloalkyl, halogen, C.sub.5-20-aryl, C.sub.6-20 aralkyl, and C(═O)R.sup.5; R.sup.5 is chosen from OR.sup.6 and N(R.sup.7).sub.2; R.sup.6 is chosen from H, and C.sub.1-20 alkyl; each R.sup.7 is independently chosen from H, C.sub.1-20 alkyl, and C.sub.6-20 aryl; each Y.sup.1 is independently chosen from halogen, C.sub.1-10-alkoxy, C.sub.5-10-aryloxy, and C.sub.1-10-carboxy; and b is an integer from 0 to 2 and (ii) one or more condensable silicon monomers; wherein the condensate and/or hydrolyzate further comprises as polymerized units one or more second unsaturated monomers free of a condensable silicon-containing moiety, wherein at least one second unsaturated monomer has the formula ##STR00036## wherein Z is chosen from an acid decomposable group, a C.sub.4-30 organic residue bound to the oxygen through a tertiary carbon, a C.sub.4-30 organic residue comprising an acetal functional group, and a monovalent organic residue having a lactone moiety; and R.sup.10 is independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, halogen, and CN, and (c) one or more crosslinkers free of Si—O linkages.

2. The composition of claim 1 wherein at least one condensable silicon monomer has the formula (8)
Si(R.sup.50).sub.p(X).sub.4-p  (8) wherein p is an integer from 0 to 3; each R.sup.50 is independently chosen from a C.sub.1-30 hydrocarbyl moiety and a substituted C.sub.1-30 hydrocarbyl moiety; and each X is independently chosen from halogen, C.sub.1-10 alkoxy, —OH, —O—C(O)—R.sup.50, and (O—Si(R.sup.51).sub.2).sub.p2—X.sup.1; X.sup.1 is independently chosen from halogen, C.sub.1-10 alkoxy, —OH, and —O—C(O)—R.sup.50; each R.sup.51 is independently chosen from R.sup.50 and X; and p2 is an integer from 1 to 10.

3. The composition of claim 2 wherein p=0 or 1.

4. (canceled)

5. The composition of claim 1 wherein L is a divalent linking group.

6. The composition of claim 5 wherein the divalent linking group is an organic radical having from 1 to 20 carbon atoms and optionally one or more heteroatoms.

7. The composition of claim 5 wherein the divalent linking group has the formula —C(═O)—O-L.sup.1- wherein L.sup.1 is a single bond or an organic radical having from 1 to 20 carbon atoms.

8-9. (canceled)

10. The composition of claim 1 wherein at least one second unsaturated monomer has an acidic proton and having a pKa in water from −5 to 13.

11. The composition of claim 9 wherein at least one second unsaturated monomer has the formula (3) ##STR00037## wherein Z is chosen from an acid decomposable group, a C.sub.4-30 organic residue bound to the oxygen through a tertiary carbon, a C4-30 organic residue comprising an acetal functional group, and a monovalent organic residue having a lactone moiety; and R.sup.10 is independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl, halogen, and CN.

12. The composition of claim 1 wherein the condensate and/or hydrolyzate further comprises as polymerized units one or more unsaturated monomers having a chromophore moiety.

13. The composition of claim 12 wherein the chromophore moiety is pendent from the polymer backbone.

14. A method comprising (a) coating a substrate with the composition of claim 1 to form a coating layer; (b) curing the coating layer to form a polymeric underlayer; (c) disposing a layer of a photoresist on the polymeric underlayer; (d) pattern-wise exposing the photoresist layer to form a latent image; (e) developing the latent image to form a patterned photoresist layer having a relief image therein; (f) transferring the relief image to the substrate; and (g) removing the polymeric underlayer by wet stripping.

15. (canceled)

16. The method of claim 14 wherein at least one condensable silicon monomer has the formula (8)
Si(R.sup.50).sub.p(X).sub.4-p  (8) wherein p is an integer from 0 to 3; each R.sup.50 is independently chosen from a C.sub.1-30 hydrocarbyl moiety and a substituted C.sub.1-30 hydrocarbyl moiety; and each X is independently chosen from halogen, C.sub.1-10 alkoxy, —OH, —O—C(O)—R.sup.50, and (O—Si(R.sup.51).sub.2).sub.p2—X.sup.1; X.sup.1 is independently chosen from halogen, C.sub.1-10 alkoxy, —OH, and —O—C(O)—R.sup.50; each R.sup.51 is independently chosen from R.sup.50 and X; and p2 is an integer from 1 to 10.

17. The method of claim 14 wherein L is a divalent linking group having the formula —C(═O)—O-L.sup.1- wherein L.sup.1 is a single bond or an organic radical having from 1 to 20 carbon atoms.

18. The method of claim 14 wherein the condensate and/or hydrolyzate further comprises as polymerized units one or more unsaturated monomers having a chromophore moiety.

Description

EXAMPLE 1

[0050] A solution of tert-butyl methacrylate (tBMA), (173 g), gamma butyrolactone (GBLMA), (166 g) and 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), (60.6 g) dissolved in 1,3-dioxolane (304 g) and a solution of V-65 initiator (60.6 g) dissolved in 2:1 v/v tetrahydrofurane/acetonitrile (60.6 g) were both added dropwise over 2 hr. to 3-dioxolane (710 g) at 75° C. under a nitrogen blanket. After addition the reaction solution was held at 75° C. for an additional two hours, cooled to room temperature and precipitated into heptanes:MTBE (1:1 v/v, 14 L). The precipitated polymer was collected by vacuum filtration and vacuum oven dried for 24 hours to afford Polymer 1 (tBMA/GBLMA/TMSPMA 50/40/10) as a white solid (271 g, 68%). M, was determined by GPC relative to polystyrene standard and was found to be 5700 Da.

EXAMPLE 2

[0051] Polymers 2 to 12, reported in Table 2 below, were synthesized according to the procedure of Example 1 using the monomers listed in Table 1 below. The amount of each monomer used is reported in Table 2 in mol %. Polymers 2 to 12 were isolated in 20-99% yield and had the M, reported in Table 2.

TABLE-US-00001 TABLE 1 [00013] [00014] [00015] [00016] [00017] [00018] [00019] [00020] [00021] [00022] [00023] [00024] [00025] [00026]

TABLE-US-00002 TABLE 2 Monomer Monomer Monomer Monomer Monomer Polymer A (mol %) B (mol %) C (mol %) D (mol %) E (mol %) M.sub.w  2 Monomer 1 Monomer 2 Monomer 3 14000  (10) (50) (40)  3 Monomer 1 Monomer 2 Monomer 3 Monomer 4 5400 (10) (50) (25) (15)  4 Monomer 1 Monomer 2 Monomer 4 Monomer 6 5100 (10) (55) (20) (15)  5 Monomer 1 Monomer 2 Monomer 3 Monomer 6 5400 (10) (50) (25) (15)  6 Monomer 1 Monomer 2 Monomer 3 Monomer 4 Monomer 6 4300 (10) (50) (25) (5) (10)  7 Monomer 1 Monomer 2 Monomer 3 4000 (10) (40) (50)  8 Monomer 1 Monomer 2 Monomer 3 Monomer 7 4000 (10) (40) (40) (10)  9 Monomer 1 Monomer 2 Monomer 3 4300 (20) (50) (30) 10 Monomer 1 Monomer 2 Monomer 3 Monomer 4 Monomer 8 4900 (10) (50) (25) (5) (10) 11 Monomer 1 Monomer 2 Monomer 5 Monomer 6 5700 (10) (50) (25) (15) 12 Monomer 1 Monomer 2 Monomer 5 Monomer 4 Monomer 6 6800 (10) (50) (25) (5) (10)

EXAMPLE 3

[0052] The procedure of Example 2 is repeated and is expected to provide Polymers 13-18 reported in Table 3. The monomer numbers reported in Table 3 refer to the monomers in Table 1 of Example 2.

TABLE-US-00003 TABLE 3 Monomer A Monomer B Monomer C Monomer D Monomer E Polymer (mol %) (mol %) (mol %) (mol %) (mol %) 13 Monomer 1 Monomer 2 Monomer 3 Monomer 4 (5) Monomer 9 (10) (50) (25) (10) 14 Monomer 2 Monomer 3 Monomer 4 Monomer 12 (45) (25) (15) (15) 15 Monomer 2 Monomer 4 Monomer 5 Monomer 8 Monomer 11 (30) (25) (25) (10) (10) 16 Monomer 4 Monomer 7 Monomer 9 (5) Monomer 11 Monomer 14 (25) (25) (10) (35) 17 Monomer 2 Monomer 3 Monomer 4 Monomer 13 (50) (25) (15) (10) 18 Monomer 1 (5) Monomer 2 Monomer 4 Monomer 5 Monomer 13 (50) (15) (20) (10)

EXAMPLE 4

[0053] A solution of hydrochloric acid (37 wt % in water, 7.76 g) in water (25.9 g) was added over 10 minutes to a mixture of TEOS (63.5 g, 50 mol %) and Polymer 1 from Example 1 (50.0 g, 50 mol %) in THF (270 g) and stirred at room temperature for 1 hr. The reaction mixture was heated to 63° C. for 20 hr. and then cooled to room temperature. PGEE (200 g) was added, the volatile species removed under reduced pressure, and the resulting solution was diluted with PGEE to provide Condensed Polymer 1 (10 wt % in PGEE, 600 g) as a clear solution. NI, was determined by GPC relative to polystyrene standards (28,100 Da).

EXAMPLE 5

[0054] Condensed Polymers 2 to 26, reported in Table 5 below, were synthesized according to the procedure of Example 4 using Polymers 1 to 12 from Examples 1 and 2 and the monomers listed in Table 4 below. The amount of each monomer used is reported in Table 5 in mol %. Condensed Polymers 2 to 12 were isolated in 20-99% yield and had the NI, reported in Table 5.

TABLE-US-00004 TABLE 4 [00027] [00028] [00029] [00030] [00031] [00032] [00033]

TABLE-US-00005 TABLE 5 Condensed Polymer Monomer A Monomer B Monomer D Polymer (mol %) (mol %) (mol %) (mol %) M.sub.w 2 1 (45) Monomer 1S 22,700 (55) 3 1 (26) Monomer 1S Monomer 2S Monomer 3S 12,400 (50)  (9) (15) 4 1 (50) Monomer 1S 52,800 (50) 5 1 (50) Monomer 1S 40,300 (50) 6 3 (50) Monomer 1S 26,600 (50) 7 2 (50) Monomer 1S 100,000 (50) 8 2 (50) Monomer 1S 30,000 (50) 9 4 (50) Monomer 1S 20,000 (50) 10 5 (50) Monomer 1S 22,000 (50) 11 6 (50) Monomer 1S 20,500 (50) 12 6 (50) Monomer 1S Monomer 2S 11,100 (40) (10) 13 9 (40) Monomer 1S Monomer 2S 25,000 (50) (10) 14 1 (40) Monomer 1S 27,700 (60) 15 1 (30) Monomer 1S 25,700 (70) 16 7 (50) Monomer 1S 29,000 (50) 17 8 (50) Monomer 1S 27,000 (50) 18 1 (60) Monomer 1S 40,600 (40) 19 9 (50) Monomer 1S 39,900 (50) 20 1 (30) Monomer 1S Monomer 2S 24,000 (65)  (5) 21 11 (50)  Monomer 1S 20,200 (50) 22 12 (50)  Monomer 1S 18,700 (50) 23 1 (50) Monomer 1S Monomer 4S 25,000 (40) (10) 24 1 (50) Monomer 1S Monomer 5S 25,000 (40) (10) 25 1 (50) Monomer 1S Monomer 6S 44,000 (40) (10) 26 1 (50) Monomer 1S Monomer 7S 24,600 (40) (10)

EXAMPLE 6

[0055] The following components were combined: 1.6 wt % of Condensed Polymer 1; 0.09 wt % of a 0.1 wt % solution of tetrabutylammonium chloride in PGEE; 49 wt % of PGEE; 49.2 wt % of 2-hydroxyisobutyric acid methyl ester; 0.009 wt % acetic acid; and 0.2 wt % coating enhancer. The mixture was filtered through 0.2 μm polytetrafluoroethylene syringe to provide Comparative Formulation 1.

EXAMPLE 7

[0056] The procedure of Example 6 was repeated to prepare Comparative Formulations 2 to 8 by replacing Condensed Polymer 1 with the Condensed Polymers reported in Table 6.

TABLE-US-00006 TABLE 6 Comparative Formulation Condensed Polymer 2 Condensed Polymer 6 3 Condensed Polymer 7 4 Condensed Polymer 23 5 Condensed Polymer 24 6 Condensed Polymer 25 7 Condensed Polymer 10 8 Condensed Polymer 11

EXAMPLE 8

[0057] The procedure of Example 6 was repeated except that Condensed Polymer 1 was replaced with a 85/15 w/w mixture of Condensed Polymer 1 and propoxylated pentaerythritol having on average 5 moles of propylene oxide (formula (11), a+b+c+d≈5) as a crosslinker to provide Formulation 1.

##STR00034##

EXAMPLE 9

[0058] The procedure of Example 6 was repeated to provide Formulations 2 to 15 by replacing Condensed Polymer 1 with the condensed polymer/crosslinker mixtures reported in Table 7. Crosslinker C1 is propoxylated pentaerythritol having on average 5 moles of propylene oxide of formula (11). Crosslinker C2 is a polymer of tert-butyl methacrylate/alpha-gammabutyrolactone methacrylate/hydroxyethyl methacrylate/methacrylic acid in a mole ratio of 25/25/25/25. Crosslinker C3 is a polymer of tert-butyl methacrylate/alpha-gammabutyrolactone methacrylate/hydroxyethyl methacrylate in a mole ratio of 50/25/25. Crosslinker C4 is polymer of methacrylic acid and hydroxyethyl methacrylate in a mole ratio of 60/40.

TABLE-US-00007 TABLE 7 Condensed Condensed Polymer/Crosslinker Formulation Polymer Crosslinker (w/w) 2 1 C1 85/15 3 1 C2 85/15 4 1 C3 85/15 5 23 C1 85/15 6 24 C1 85/15 7 25 C1 85/15 8 6 C1 85/15 9 7 C1 85/15 10 10 C1 85/15 11 10 C4 85/15 12 11 C4 95/5  13 11 C4 90/10 14 11 C4 85/15 15 11 C1 85/15

EXAMPLE 10

[0059] Comparative Formulations from Examples 6 and 7 and Formulations of the invention from Examples 8 and 9 were spin-coated on a bare 200 mm silicon wafers at 1500 rpm and baked at 240° C. for 60 seconds using an ACT-8 Clean Track (Tokyo Electron Co.). The thickness of each coated film after baking of was measured with an OptiProbe™ instrument from Therma-wave Co. Each coated sample was then evaluated for SC-1 wet strippability using a 1/1/40 wt/wt/wt mixture of 30% NH.sub.4OH/30% H.sub.2O.sub.2/water. The SC-1 mixture was heated to 60° C., and coupons of each coated wafer were immersed into the solution for 1 min. The coupons were removed from the SC-1 mixture and rinsed with deionized water, and the film thickness was again measured. The film thickness loss for each sample was calculated as the difference in film thickness before and after contact with the stripping agent. A separate film prepared as described above was optionally tested for SC-1 strippability after etching. Etching was performed for 60 seconds using RIE790 from Plasma-Therm Co. with oxygen gas, 25 sscm flow, 180 W of power, and 6 mTorr of pressure. The stripping results, obtained as the rate of film removal in A/min, are reported in Table 8.

[0060] Comparative Formulations from Examples 6 and 7 and Formulations of the invention from Examples 8 and 9, at either 1.7% or 3.5% solids, were coated on 200 mm silicon wafers as described above with a target thickness of 400 Å or 1000 Å and measured (post cure) as described above. A puddle of commercially available 0.26N TMAH developer (MF CD-26) was applied to each wafer for 60 seconds, after which the wafers were rinsed with DI water, spin dried and the film thickness was re-measured. A final drying bake of 105° C./60 seconds was applied to each wafer and final film thickness was measured. The thickness loss of each film, reported as the rate of film removal in A/min, resulting from this TMAH strip is reported in Table 8. A negative film strip value indicates an increase in film thickness.

TABLE-US-00008 TABLE 8 Before Etch After Etch TMAH Strip Formulation Example (Å/min) (Å/min) (Å/min) Comparative Formulation 1 >394 >242 −41 1 905 546 −10 2 754 415 −4 3 807 475 −4 4 759 422 −9 Comparative Formulation 2 409 466 −19 8 210 423 −4 Comparative Formulation 3 190 452 −50 9 140 184 −7 Comparative Formulation 4 110 114 −25 5 38 96 −3 Comparative Formulation 5 87 99 −21 6 64 84 −2 Comparative Formulation 6 90 98 −6 7 74 89 −2 Comparative Formulation 7 113 409 −13 10 41 145 0 11 116 381 −4 Comparative Formulation 8 226 428 −16 12 158 433 −12 13 134 414 −2 14 86 194 0 15 89 395 1