Method using 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; and (b) a condensate and/or hydrolyzate of (i) one or more 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, one or more second unsaturated monomers having a chromophore moiety, and one or more third unsaturated monomers being free of a condensable silicon-containing moiety and having the formula (3) ##STR00038## 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, halo, and CN, and (ii) one or more condensable silicon monomers, wherein the one or more polymers are free of a pendent aromatic ring having a substituent of the formula ##STR00039## where each Rx is independently H or a alkyl group of 1 to 15 carbons, where each Rx may be taken together form an aliphatic ring; Lg is H, an aliphatic monovalent hydrocarbon having 1 to 10 carbons, or a monovalent aromatic group; a1=0 or 1; and * indicates the point of attachment to the aromatic ring.

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 halo, 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 halo, C.sub.1-10 alkoxy, —OH, —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 1 wherein the condensable silicon-containing moiety has the formula
*-L-SiR.sup.1.sub.bY.sup.1.sub.3-b wherein L is a single covalent bond or a divalent linking group; each R.sup.1 is independently chosen from H, C.sub.1-10-alkyl, C.sub.2-20-alkenyl, C.sub.5-20-aryl, and C.sub.6-20-aralkyl; each Y.sup.1 is independently chosen from halogen, C.sub.1-10-alkoxy, C.sub.5-10-aryloxy, C.sub.1-10-carboxy; b is an integer from 0 to 2; and * denotes the point of attachment to the polymer backbone.

4. The composition of claim 3 wherein L is a divalent linking group.

5. The composition of claim 4 wherein the divalent linking group comprises one or more heteroatoms chosen from oxygen and silicon.

6. The composition of claim 4 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 3 wherein the divalent linking group has the formula —C(═O)—O-L.sup.1- wherein L.sup.1 is a single covalent bond or an organic radical having from 1 to 20 carbon atoms.

8. The composition of claim 1 wherein at least one first unsaturated monomer has the formula (1) ##STR00040## wherein L is a single covalent bond or a divalent linking group; each R.sup.1 is independently chosen from H, C.sub.1-10-alkyl, C.sub.2-20-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, halo, 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, halo, 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, C.sub.1-10-carboxy; and b is an integer from 0 to 2.

9. The composition of claim 1 wherein the condensate and/or hydrolyzate further comprises as polymerized units one or more unsaturated monomers free of a condensable silicon-containing moiety having an acidic proton and having a pKa in water from −5 to 13.

10. The composition of claim 1 wherein the chromophore moiety is pendent from the polymer backbone.

11. The composition of claim 10 wherein the chromophore moiety is chosen from pyridyl, phenyl, naphthyl, acenaphthyl, fluorenyl, carbazolyl, anthracenyl, phenanthryl, pyrenyl, coronenyl, tetracenyl, pentacenyl, tetraphenyl, benzotetracenyl, triphenylenyl, perylenyl, benzyl, phenethyl, tolyl, xylyl, styrenyl, vinylnaphthyl, vinylanthracenyl, dibenzothiophenyl, thioxanthonyl, indolyl, and acridinyl.

12. A method comprising (a) coating a substrate with a composition of claim 1; (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.

13. The method of claim 12 wherein the polymeric underlayer is removed by wet stripping.

14. The method of claim 12 further comprising disposing a bottom antireflective coating layer directly on the polymeric underlayer and then curing the antireflective coating layer and then disposing the photoresist layer directly on the cured antireflective coating layer.

Description

COMPARATIVE EXAMPLE 1

(1) 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), tetraethyl orthosilicate (294 g) and 2-propanol (467 g) over 10 minutes. The reaction mixture was stirred at room temperature for 1 hour, heated to reflux for 24 hours and cooled to room temperature. The solution was diluted with propylene glycol monoethyl ether (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 Comparative Polymer 1 (M.sub.w=9000 Da).

EXAMPLE 1: PREPARATION OF POLYMER 1

(2) 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 hours 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.sub.w was determined by GPC relative to polystyrene standard and was found to be 5700 Da.

EXAMPLE 2

(3) Polymers 2 to 12 and Comparative Polymers 2 to 4, 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.sub.w reported in Table 2.

(4) TABLE-US-00001 TABLE 1 Monomer 1 Monomer 2 Monomer 3 0 Monomer 4 Monomer 5 Monomer 6 Monomer 7 Monomer 8 Monomer 9 Monomer 10 Monomer 11 Monomer 12 Monomer 13 0 Monomer 14

(5) TABLE-US-00002 TABLE 2 Monomer A Monomer B Monomer C Monomer D Monomer E Polymer (mol %) (mol %) (mol %) (mol %) (mol %) M.sub.w Comparative Monomer 4 Monomer 7 4000 Polymer 2 (40) (60) Comparative Monomer 2 Monomer 3 Monomer 4 4000 Polymer 3 (50) (25) (25) Comparative Monomer 2 Monomer 3 Monomer 4 Monomer 10 4000 Polymer 4 (25) (25) (25) (25) 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

(6) 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.

(7) 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

(8) 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 hour. The reaction mixture was heated to 63° C. for 20 hours 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 deliver Condensed Polymer 1 (10 wt % in PGEE, 600 g) as a clear solution. M.sub.w was determined by GPC relative to polystyrene standard (28,100 Da).

EXAMPLE 5

(9) 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 M.sub.w reported in Table 5.

(10) TABLE-US-00004 TABLE 4 Monomer 1S Monomer 2S Monomer 3S Monomer 4S Monomer 5S Monomer 6S Monomer 7S

(11) TABLE-US-00005 TABLE 5 Con- Monomer densed Polymer Monomer A Monomer B 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 12,400 (50) (9) 3S (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 5S 44,000 (40) (10) 26 1 (50) Monomer 1S Monomer 7S 24,600 (40) (10)

EXAMPLE 6

(12) The following components were combined: 3.277 g of Condensed Polymer 2 as component 1; 0.77 g of a 0.1 wt % solution of tetrabutylammonium chloride in PGEE as component 2; 4.325 g of PGEE as component 3; and 8.85 g of 2-hydroxyisobutyric acid methyl ester as component 4. The mixture was filtered through 0.2 μm polytetrafluoroethylene syringe to provide Formulation 1.

EXAMPLE 7

(13) The procedure of Example 6 was repeated to prepare Formulations 2 to 26 reported in Table 6. In Table 6, Component 1 refers to the polymer added to each Formulation, Component 2 is 0.1 wt % solution of tetrabutylammonium chloride in PGEE, Component 3 is PGEE, and Component 4 is 2-hydroxyisobutyric acid methyl ester. Component 5 is a 10 wt % solution of any Comparative Polymer in an organic solvent.

(14) TABLE-US-00006 TABLE 6 Amount of Amount of Amount of Component 1 Component 2 Component 3 Component 4 Component 5 Formulation (g) (g) (g) (g) (g) Comparative Comparative 0.640 5.66 8.24 Formulation 1 Polymer 1 (2.38) Comparative Comparative 0.777 5.36 7.81 Comparative Formulation 2 Polymer 1 Polymer 2 (1.73) (1.15) Comparative Comparative 0.480 18.0 3.95 Comparative Formulation 3 Polymer 1 Polymer 3 (3.10) (0.665) Comparative Comparative 1.07 67.9 79.0 Comparative Formulation 4 Polymer 1 Polymer 4 (19.8) (19.8) 2 Condensed 0.777 3.93 8.85 Polymer 2 (3.28) 3 Condensed 0.777 4.33 8.85 Polymer 3 (2.88) 4 Condensed 8.64 37.7 98.3 Polymer 4 (42.4) 5 Condensed 0.777 4.33 8.85 Polymer 5 (2.88) 6 Condensed 0.777 4.33 8.85 Polymer 6 (2.88) 7 Condensed 0.777 4.33 8.85 Polymer 7 (2.88) 8 Condensed 0.777 4.33 8.85 Polymer 8 (2.88) 9 Condensed 0.777 4.33 8.85 Polymer 9 (2.88) 10 Condensed 0.777 4.33 8.85 Polymer 10 (2.88) 11 Condensed 0.777 4.33 8.85 Polymer 11 (2.88) 12 Condensed 0.777 4.33 8.85 Polymer 12 (2.88) 13 Condensed 0.777 4.33 8.85 Polymer 13 (2.88) 14 Condensed 0.777 3.47 8.85 Polymer 14 (3.74) 15 Condensed 0.777 4.33 8.85 Polymer15 (2.88) 16 Condensed 0.777 4.33 8.85 Polymer 16 (2.88) 17 Condensed 0.777 4.33 8.85 Polymer 17 (2.88) 18 Condensed 0.777 4.33 8.85 Polymer 18 (2.88) 19 Condensed 0.777 4.33 8.85 Polymer 19 (2.88) 20 Condensed 0.777 4.33 8.85 Polymer 20 (2.88) 21 Condensed 0.777 4.33 8.85 Polymer 21 (2.88) 22 Condensed 0.777 4.33 8.85 Polymer 22 (2.88) 23 Condensed 0.777 4.24 8.85 Polymer 23 (2.96) 24 Condensed 0.777 4.33 8.85 Polymer 24 (2.88) 25 Condensed 0.777 4.33 8.85 Polymer 25 (2.88) 26 Condensed 0.777 4.33 8.85 Polymer 26 (2.45)

EXAMPLE 8

(15) Formulations from Example 7 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 70° C., and coupons of each coated wafer were immersed into the solution for 5 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 Å/min, are reported in Table 7. A stripping rate of 0 to 1 Å/min. was considered as “no etch”. In Table 7, “⋄” denotes a stripping rate of >1 to 10 Å/min, “.square-solid.” denotes a stripping rate of >10 to 50 Å/sec, “□” denotes a stripping rate of >50 to 100 Å/min, “.box-tangle-solidup.” denotes a stripping rate of >100 to 250 Å/min, and “Δ” denotes a stripping rate of >250 Å/min.

(16) TABLE-US-00007 TABLE 7 Formulation Example Before Etch (Å/min) After Etch (Å/min) Comparative Formulation 1 No etch No etch Comparative Formulation 2 ⋄ .square-solid. Comparative Formulation 3 □ .square-solid. Comparative Formulation 4 ⋄ □ 2 Δ .box-tangle-solidup. 3 .box-tangle-solidup. .square-solid. 4 Δ Δ 5 Δ Δ 6 Δ Δ 7 .box-tangle-solidup. Δ 8 .box-tangle-solidup. Δ 9 □ .box-tangle-solidup. 10 .box-tangle-solidup. .box-tangle-solidup. 11 Δ .box-tangle-solidup. 12 ⋄ .box-tangle-solidup. 13 □ .box-tangle-solidup. 14 Δ Δ 15 Δ Δ 16 Δ Δ 17 .box-tangle-solidup. Δ 18 Δ Δ 19 .box-tangle-solidup. .box-tangle-solidup. 20 Δ Δ 21 .box-tangle-solidup. Δ 22 .box-tangle-solidup. Δ 23 .square-solid. □ 24 □ □ 25 □ □ 26 .box-tangle-solidup. Δ

COMPARATIVE EXAMPLE 2

(17) 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 hours 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 Comparative Polymer 5 (tBMA/GBLMA/TMSPMA 50/40/10) as a white solid (271 g, 68%). M.sub.w was determined by GPC relative to polystyrene standard and was found to be 5700 Da.

(18) Comparative Polymer 5 (15 g, 91.5 mmol) and 35 g of tetrahydrofuran (THF) were added to a 250 mL 3-necked round bottom flask equipped with a thermocouple, an overhead stirrer, a water-cooling condenser, an addition funnel, a N.sub.2 feed line, a bubbler, and a heating mantle. The mixture was stirred at room temperature until all the polymer was dissolved. In a separate container, hydrochloric acid (0.122 g, 1.235 mmol) and DI water (0.816 g, 45.2 mmol) were mixed together. The aqueous acid solution was charged to the reactor via addition funnel over 10 min at ambient temperature. The mixture was stirred at ambient temperature for 1 hr. Then, the temperature was adjusted to 63±2° C. over 30 minutes to initiate reflux. The solution was stirred at reflux temperature for 4 hr. The reaction mixture was allowed to cool to room temperature overnight with continued stirring. Next, the solution was diluted with PGEE and concentrated on a rotary evaporator under reduced pressure to provide Condensed Comparative Polymer 5. The solution was treated with Amberlite IRN150 ion exchange resin (10 wt % of final weight) by rolling for 1 hr., filtered using 0.2 polytetrafluoroethylene (PTFE) filter, and stored in a plastic container at −10° C. Analysis of Condensed Comparative Polymer 5 provided a M.sub.w of 51,000 Da, and a PDI of 4.3.

EXAMPLE 9

(19) Films A-E were prepared by dispensing the compositions indicated in Table 8 below into separate three inch aluminum pans. Condensed Comparative Polymer 5 from Comparative Example 2 does not contain a separate condensable silicon monomer. Films C and E were formed from compositions containing tetraethylorthosilicate (“TEOS”) which was not condensed with the polymer prior to being dispensed into the pan. The TEOS used in the formulations of Films C and W was an attempt to cure the film in-situ. The films were visually inspected for coating quality. The coating quality of the films is also reported in Table 8. Films C and E were heterogeneous, showing phase separation and non-uniformity, making such films unsuitable for underlayer applications.

(20) TABLE-US-00008 TABLE 8 Condensable Silicon Film Polymer (g) Monomer (g) Solvent (g) Coating Quality A - Comparative Polymer 1 (0.10) — PGEE (0.90) Homogeneous B - Comparative Condensed — — Homogeneous Comparative Polymer 5 (1.0) C - Comparative Condensed TEOS (0.5) — Heterogeneous Comparative Polymer 5 (0.5) D - Invention Condensed — — Homogeneous Polymer 5 (1.0) E - Comparative Polymer 1 (0.05) TEOS (0.5) PGEE (0.045) Heterogeneous

(21) Following visual inspection, each of the pans containing Films A to E was heated to 110° C. for 60 min. and the dried film was scraped off and analyzed by FTIR. The total FTIR peak area from 1770-1850 cm.sup.−1 and from 1769-1650 cm.sup.−1 for each of the films was integrated. Table 9 represents these areas as a percentage of the total peak area. These are the C═O bond stretch regions in the IR spectra and are indicative of film structure. Differences in these percentages indicate differences in the films. The data in Table 9 clearly show that Films A-C and E are similar to each other in structure as they have similar percentages of peak area in both regions, however Film D has a significantly higher percentage of peak area in the 1769-1650 cm.sup.−1 range, indicating that Film D has a different film structure from the other films. Film D also has a stretch between 3000-3500 cm.sup.−1 corresponding to silanol which is missing in the spectra of the other films. It is clear from the film quality, C═O integration, and the stretch between 3000-3500 cm.sup.−1 that Film D is different from Films A-C and E.

(22) TABLE-US-00009 TABLE 9 Integration 1770-1850 Integration 1769-1650 Film (cm.sup.−1) (cm.sup.−1) A - Comparative 36% 64% B - Comparative 33% 67% C - Comparative 32% 68% D - Invention 18% 82% E - Comparative 38% 62%

EXAMPLE 10

(23) The formulations reported in Table 10 were prepared according to the procedure of Example 7, where Components 2, 3 and 4 are as defined in Example 7. In addition, each formulation contained 0.6 g of a coating enhancer and 0.38 g of carboxylic acids. Comparative Polymer 5 (from U.S. Pat. No. 8,932,953) was a condensation product of a t-butoxystyrene/TMSPMA (90/10) as a first component and a condensation product of TEOS as a second component, in a 1:1 ratio of first component to second component. Polymer 27 was tBMA/GBLMA/HEMA/BzMA/TMSPMA (50/25/5/10/10) and was prepared according to the general procedure of Example 1, where HEMA=hydroxyethyl methacrylate and BzMA=benzyl methacrylate. Polymer 27 was determined to have a M.sub.w of 4010, and a PDI of 1.7. Condensed Polymer 27 was prepared according to the procedure of Example 4 using 50/50 molar amounts of Polymer 27 and TEOS, and was determined to have a M.sub.w of 50,000, and a PDI of 4.1.

(24) Formulations 27 and 28, and Comparative Formulation 5 were evaluated for strippability before etching according to the procedure of Example 8. The stripping results, obtained as the rate of film removal in Å/min, are reported in Table 10, where a negative number indicates swelling of the film.

(25) TABLE-US-00010 TABLE 10 Amount of Amount of Amount of Component 1 Component 2 Component 3 Component 4 Before Etch Formulation (g) (g) (g) (g) (Å/min) Comparative Comparative 0.65 3.60 7.37 −49 Formulation 5 Polymer 5 (2.40) Formulation Condensed 0.65 3.60 7.37 >714 27 Polymer 1 (2.4) Formulation Condensed 0.65 3.60 7.37 >780 28 Polymer 27 (2.40)