Silicon-containing underlayers

Abstract

Methods of manufacturing electronic devices employing wet-strippable underlayer compositions comprising one or more condensed polymers having an organic polymer chain having pendently-bound moieties having an acidic proton and a pKa in water from −5 to 13 and having pendently-bound siloxane moieties are provided.

Claims

1. A composition comprising: (a) one or more solvents; and (b) a condensate and/or hydrolyzate of (i) one or more organic polymers comprising as polymerized units: one or more first unsaturated monomers having a moiety having an acidic proton and a pKa in water from −5 to 13; one or more second unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to the organic polymer backbone; one or more third unsaturated monomers free of an acidic moiety having an acidic proton and having a pKa in water of −5 to 13, and free of a condensable silicon-containing moiety, wherein at least one third monomer has the formula (5) ##STR00012## wherein ADG is an acid decomposable group; and R.sup.21 is H, C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, halogen, or CN; and one or more unsaturated monomers having a chromophore moiety, and (ii) one or more condensable silicon monomers.

2. The composition of claim 1 wherein at least one first unsaturated monomer has an acidic moiety selected from the group consisting of carboxylic acid, sulfonic acid, sulfinic acid, sulfamic acid, boronic acid, phosphoric acid, and combinations and acid salts thereof, a hydroxyaryl group, an unsubstituted imide group, a mercapto group, and a C.sub.1-20-hydroxyl-substituted haloalkyl group.

3. The composition of claim 1 wherein at least one first unsaturated monomer has the formula (1) ##STR00013## wherein L.sup.1 is a single bond or a divalent linking group; AM is an acidic moiety having an acidic proton and having a pKa in water from −5 to 13; each of R.sup.1 and R.sup.2 is independently H, C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, optionally substituted C.sub.6-20-aryl, halogen, or CN; R.sup.3 is H, C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, optionally substituted C.sub.6-20-aryl, halogen, or —C(═O)R.sup.4; R.sup.4 is OR.sup.5 or N(R.sup.6).sub.2; R.sup.5 is H, C.sub.1-20-alkyl, C.sub.5-30-aryl, C.sub.6-20-aralkyl or a monovalent organic residue having a lactone moiety; and each R.sup.6 is independently H, C.sub.1-20-alkyl, or C.sub.6-20-aryl; wherein any two of L.sup.1, R.sup.1, R.sup.2 and R.sup.3 may be taken together with the carbons to which they are attached to form a 5 to 7-membered ring.

4. The composition of claim 3 wherein L.sup.1 is a single covalent bond or a divalent organic radical having from 1 to 20 carbon atoms and optionally one or more heteroatoms.

5. The composition of claim 1 wherein the condensable silicon-containing moiety has the formula (2)
*-L.sup.2-SiR.sup.7.sub.bY.sup.1.sub.3-b  (2) wherein L.sup.2 is a single bond or a divalent linking group; each R.sup.7 is independently H, C.sub.1-10-alkyl, C.sub.2-20-alkenyl, C.sub.5-20-aryl, or C.sub.6-20-aralkyl; each Y.sup.1 is independently halogen, C.sub.1-10-alkoxy, C.sub.5-10-aryloxy, or C.sub.1-10-carboxy; b is an integer from 0 to 2; and * denotes the point of attachment to the monomer.

6. The composition of claim 1 wherein at least one second unsaturated monomer has the formula (3) ##STR00014## wherein L.sup.2 is a single bond or a divalent linking group; each R.sup.7 is independently H, C.sub.1-10-alkyl, C.sub.2-20-alkenyl, C.sub.5-20-aryl, or C.sub.6-20-aralkyl; each of R.sup.8 and R.sup.9 is independently H, C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, halogen, C.sub.5-20-aryl, C.sub.6-20-aralkyl, or CN; R.sup.10 is H, C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, halogen, C.sub.5-20-aryl, C.sub.6-20-aralkyl, or C(═O)R.sup.11; R.sup.11 is OR.sup.12 or N(R.sup.13).sub.2; R.sup.12 is H, C.sub.1-20 alkyl, C.sub.5-20-aryl, or C.sub.6-20-aralkyl; each R.sup.13 is independently H, C.sub.1-20-alkyl, or C.sub.5-20-aryl; each Y.sup.1 is independently halogen, C.sub.1-10-alkoxy, C.sub.5-10-aryloxy, or C.sub.1-10-carboxy; and b is an integer from 0 to 2.

7. The composition of claim 6 wherein L.sup.2 is a divalent organic radical having from 1 to 20 carbon atoms and optionally one or more heteroatoms.

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

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

10. The composition of claim 9 wherein the chromophore moiety is selected from the group consisting of from furyl, pyryl, thiophenyl, 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.

11. The composition of claim 1 wherein at least one condensable silicon monomer has the formula (9)
Si(R.sup.50).sub.p(X).sub.4-p  (9) wherein each R.sup.50 is independently a C.sub.1-30 hydrocarbyl moiety or a substituted C.sub.1-30 hydrocarbyl moiety; and each X is independently halogen, C.sub.1-10 alkoxy, —OH, —O—C(O)—R.sup.50, —(O—Si(R.sup.51).sub.2).sub.p2—X.sup.1, or —(Si(R.sup.51).sub.2).sub.p3—X.sup.1; X.sup.1 is independently halogen, C.sub.1-10 alkoxy, —OH, or —O—C(O)—R.sup.50; each R.sup.51 is independently R.sup.50 or X; p is an integer from 0 to 3; p2 is an integer from 1 to 10; and p3 is an integer from 1 to 10.

12. The composition of claim 11 wherein p=0 or 1.

13. A method comprising (a) coating a substrate with a composition to form a coating layer, wherein the composition comprises: (1) one or more solvents; and (2) a condensate and/or hydrolyzate of (i) one or more organic polymers comprising as polymerized units: one or more first unsaturated monomers having a moiety having an acidic proton and a pKa in water from −5 to 13; one or more second unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to the organic polymer backbone; and one or more third unsaturated monomers free of an acidic moiety having an acidic proton and having a pKa in water of −5 to 13, and free of a condensable silicon-containing moiety, wherein at least one third monomer has the formula (5) ##STR00015## wherein ADG is an acid decomposable group; and R.sup.21 is H, C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, halogen, or CN, and (ii) one or more condensable silicon monomers; (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; (0 transferring the relief image to the substrate; and (g) removing the polymeric underlayer by wet stripping.

14. The method of claim 13 wherein the organic polymer further comprises as polymerized units one or more unsaturated monomers having a chromophore moiety.

15. The method of claim 13 wherein the polymeric underlayer is removed by wet stripping at room temperature.

Description

EXAMPLE 1

(1) A solution of tert-butyl methacrylate (tBMA), (59.99 g), methacrylic acid (MAA), (29.06 g) and 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), (20.95 g) dissolved in 1,3-dioxolane (85.4 g) and a solution of V-65 initiator (20.95 g) dissolved in 2:1 v/v tetrahydrofurane/acetonitrile (20.9 g) were both added dropwise over 2 hours to 1,3-dioxolane (199 g) at 75° C. under a nitrogen blanket. After addition, the reaction mixture was held at 75° C. for an additional two hours, cooled to room temperature and precipitated into heptanes (3.8 L). The precipitated polymer was collected by vacuum filtration and vacuum oven dried for 24 hours to afford Polymer 1 (tBMA/MAA/TMSPMA 50/40/10) as a white solid (99 g, 90%). M.sub.w was determined by GPC relative to polystyrene standards and was found to be 7828 Da.

EXAMPLE 2

(2) A solution of hydrochloric acid (37 wt % in water, 2.93 g) in water (9.8 g) was added over 10 minutes to a mixture of tetraethyl orthosilicate (TEOS) (23.97 g, 50 mol %) and Polymer 1 from Example 1 (15.0 g, 50 mol %) in tetrahydrofuran (THF) (81 g) and stirred at room temperature for 1 hour. The reaction mixture was heated to 63° C. for 4 hours and then cooled to room temperature. PGEE (107 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, 213 g) as a clear solution. M.sub.w was determined by GPC relative to polystyrene standards and was found to be 29,300 Da.

EXAMPLE 3

(3) A solution of hydrochloric acid (37 wt % in water, 0.92 g) in water (3.06 g) was added over 10 minutes to a mixture of TEOS (6.85 g, 30 mol %) and Polymer 1 from Example 1 (10.0 g, 70 mol %) in THF (39 g) and stirred at room temperature for 1 hour. The reaction mixture was heated to 63° C. for 6 hours and then cooled to room temperature. PGEE (52 g) was added, the volatile species removed under reduced pressure, and the resulting solution was diluted with PGEE to deliver Condensed Polymer 2 (10 wt % in PGEE, 125 g) as a clear solution. M.sub.w was determined by GPC relative to polystyrene standards and was found to be 35,000 Da.

EXAMPLE 4

(4) A solution of hydrochloric acid (37 wt % in water, 6.56 g) in water (21.9 g) was added over 10 minutes to a mixture of TEOS (55.93 g, 70 mol %) and Polymer 1 from Example 1 (15.0 g, 30 mol %) in THF (81 g) and stirred at room temperature for 1 hour. The reaction mixture was heated to 63° C. for 6 hours and then cooled to room temperature. PGEE (107 g) was added, the volatile species removed under reduced pressure, and the resulting solution was diluted with PGEE to deliver Condensed Polymer 3 (10 wt % in PGEE, 342 g) as a clear solution. M.sub.w was determined by GPC relative to polystyrene standards and was found to be 27,000 Da.

EXAMPLE 5

(5) A solution of hydrochloric acid (37 wt % in water, 1.08 g) in water (3.61 g) was added over 10 minutes to a mixture of TEOS (7.38 g, 30 mol %), phenyltrimethoxysilane (PTMS) (1.17 g, 5 mol %) and Polymer 1 from Example 1 (10.0 g, 65 mol %) in THF (40.5 g) and stirred at room temperature for 1 hour. The reaction mixture was heated to 63° C. for 6 hours and then cooled to room temperature. PGEE (55 g) was added, the volatile species removed under reduced pressure, and the resulting solution was diluted with PGEE to deliver Condensed Polymer 4 (10 wt % in PGEE, 121 g) as a clear solution. M.sub.w was determined by GPC relative to polystyrene standards and was found to be 21,000 Da.

COMPARATIVE EXAMPLE 1

(6) 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:methyl tert-butyl ether (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 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 7

(7) Formulations were prepared by combining: 1.60 wt % of the condensed polymer indicated in Table 1; 0.004 wt % of a 0.1 wt % solution of tetrabutylammonium chloride in PGEE; 48.95 wt % of PGEE; 49.15 wt % of 2-hydroxyisobutyric acid methyl ester; 0.009 wt % of malonic acid; 0.085 wt % of acetic acid; and 0.2 wt % of a long chain alcohol coating enhancer. Each formulation was filtered through 0.2 m polytetrafluoroethylene syringe.

(8) TABLE-US-00001 TABLE 1 Condensed Polymer Formulation Sample Comparative Polymer 1 Comparative Formulation 1 Condensed Polymer 1 Formulation 1 Condensed Polymer 2 Formulation 2 Condensed Polymer 3 Formulation 3 Condensed Polymer 4 Formulation 4

EXAMPLE 8

(9) 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 was measured with an OptiProbe™ instrument from Therma-wave Co. Each coated sample was then evaluated for SC-1 wet strippability using an SC-1 solution of 1/8/50 wt/wt/wt mixture of 30% NH.sub.4OH/30% H.sub.2O.sub.2/water. The SC-1 solution was heated to 25° C., and coupons of each coated wafer were immersed into the solution for 1 min. The coupons were removed from the SC-1 solution 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 SC-1 solution. 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 1.

(10) Formulation samples from Example 7, 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 Å/min, resulting from this TMAH strip is reported in Table 2. A negative film strip value indicates an increase in film thickness.

(11) TABLE-US-00002 TABLE 2 Formulation Before Etch After Etch TMAH Strip Example (Å/min) (Å/min) (Å/min) Comparative Formulation 1 15 47 −14 Formulation 1 104 78 6 Formulation 2 361 225 19 Formulation 3 171 45 7 Formulation 4 169 33 —