AROMATIC UNDERLAYER

Abstract

Compounds having three or more alkynyl moieties substituted with an aromatic moiety having one or more of certain substituents are useful in forming underlayers useful in semiconductor manufacturing processes.

Claims

1. A method comprising: (a) providing an electronic device substrate; (b) coating a layer of a coating composition comprising one or more curable compounds on a surface of the electronic device substrate, wherein the one or more curable compounds comprise an aromatic core chosen from a C.sub.5-6 aromatic ring and a C.sub.9-30 fused aromatic ring system and three or more substituents of formula (1) ##STR00024## wherein at least two substituents of formula (1) are attached to the aromatic core; and wherein Ar.sup.1 is an aromatic ring or fused aromatic ring system having from 5 to 30 carbons; Z is a substituent chosen from OR.sup.1, protected hydroxyl, carboxyl, protected carboxyl, SR.sup.1, protected thiol, OC(O)C.sub.1-6-alkyl, halogen, and NHR.sup.2; each R.sup.1 is chosen from H, C.sub.1-10 alkyl, C.sub.2-10 unsaturated hydrocarbyl, and C.sub.5-30 aryl; each R.sup.2 is chosen from H, C.sub.1-10 alkyl, C.sub.2-10 unsaturated hydrocarbyl, C.sub.5-30 aryl, C(O)R.sup.1, and S(O).sub.2R.sup.1; x is an integer from 1 to 4; and * denotes the point of attachment to the aromatic core; (c) curing the layer of the curable compound to form an underlayer; (d) coating a layer of a photoresist on the underlayer; (e) exposing the photoresist layer to actinic radiation through a mask; (f) developing the exposed photoresist layer to form a resist pattern; and (g) transferring the pattern to the underlayer to expose portions of the electronic device substrate.

2. The method of claim 1 further comprising the steps of patterning the substrate; and then removing the patterned underlayer.

3. The method of claim 1 further comprising the step of coating one or more of a silicon-containing layer, an organic antireflective coating layer and a combination thereof over the underlayer before step (d).

4. The method of claim 3 further comprising the step of transferring the pattern to the one or more of the silicon-containing layer, the organic antireflective coating layer and the combination thereof after step (f) and before step (g).

5. The method of claim 1 wherein each Z is independently chosen from OR.sup.1, protected hydroxyl, carboxyl, protected carboxyl, SH, fluorine and NHR.sup.2.

6. The method of claim 1 wherein aromatic core is chosen from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, and benzo[a]pyrene.

7. The method of claim 1 wherein each Ar.sup.1 is independently chosen from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, and benzo[a]pyrene.

8. The method of claim 1 wherein the coating composition further comprises one or more of an organic solvent, a curing agent, and a surface leveling agent.

9. An electronic device comprising an electronic device substrate having a layer of a polymer comprising as polymerized units one or more curable compounds on a surface of the electronic device substrate, wherein the one or more curable compounds comprise an aromatic core chosen from a C.sub.5-6 aromatic ring and a C.sub.9-30 fused aromatic ring system and three or more substituents of formula (1) ##STR00025## wherein at least two substituents of formula (1) are attached to the aromatic core; and wherein Ar.sup.1 is an aromatic ring or fused aromatic ring system having from 5 to 30 carbons; Z is a substituent chosen from OR.sup.1, protected hydroxyl, carboxyl, protected carboxyl, SR.sup.1, protected thiol, OC(O)C.sub.1-6-alkyl, halogen, and NHR.sup.2; each R.sup.1 is chosen from H, C.sub.1-10 alkyl, C.sub.2-10 unsaturated hydrocarbyl, and C.sub.5-30 aryl; each R.sup.2 is chosen from H, C.sub.1-10 alkyl, C.sub.2-10 unsaturated hydrocarbyl, C.sub.5-30 aryl, C(O)R.sup.1, and S(O).sub.2R.sup.1; x is an integer from 1 to 4; and * denotes the point of attachment to the aromatic core.

10. A compound of formula (2) ##STR00026## wherein Ar.sup.c is an aromatic core having from 5 to 30 carbon atoms; Ar.sup.1, Ar.sup.2, and Ar.sup.3 are each independently an aromatic ring or fused aromatic ring system having from 5 to 30 carbons; Y is a single covalent chemical bond, a divalent linking group, or a trivalent linking group; Z.sup.1 and Z.sup.2 are independently a substituent chosen from OR.sup.1, protected hydroxyl, carboxyl, protected carboxyl, SR.sup.1, protected thiol, OC(O)C.sub.1-6-alkyl, halogen, and NHR.sup.2; each R.sup.1 is chosen from H, C.sub.1-10 alkyl, C.sub.2-10 unsaturated hydrocarbyl, and C.sub.5-30 aryl; each R.sup.2 is chosen from H, C.sub.1-10 alkyl, C.sub.2-10 unsaturated hydrocarbyl, C.sub.5-30 aryl, C(O)R.sup.1, and S(O).sub.2R.sup.1; x1=1 to 4; x2=1 to 4; y1=2 to 4; each y2=0 to 4; y1+each y23; w=0 to 2; and z equals 0 to 2; wherein z=1 when Y is a single covalent chemical bond or a divalent linking group; and z=2 when Y is a trivalent linking group; provided that Ar.sup.c and each Ar.sup.1 are not phenyl when w=0.

11. A method comprising: (a) providing an electronic device substrate; (b) coating a layer of a coating composition comprising one or more curable compounds of formula (2) ##STR00027## wherein Ar.sup.c is an aromatic core having from 5 to 30 carbon atoms; Ar.sup.1, Ar.sup.2, and Ar.sup.3 are each independently an aromatic ring or fused aromatic ring system having from 5 to 30 carbons; Y is a single covalent chemical bond, a divalent linking group, or a trivalent linking group; Z.sup.1 and Z.sup.2 are independently a substituent chosen from OR.sup.1, protected hydroxyl, carboxyl, protected carboxyl, SR.sup.1, protected thiol, OC(O)C.sub.1-6-alkyl, halogen, and NHR.sup.2; each R.sup.1 is chosen from H, C.sub.1-10 alkyl, C.sub.2-10 unsaturated hydrocarbyl, and C.sub.5-30 aryl; each R.sup.2 is chosen from H, C.sub.1-10 alkyl, C.sub.2-10 unsaturated hydrocarbyl, C.sub.5-30 aryl, C(O)R.sup.1, and S(O).sub.2R.sup.1; x1=1 to 4; x2=1 to 4; y1=2 to 4; each y2=0 to 4; y1+each y23; w=0 to 2; and z equals 0 to 2; wherein z=1 when Y is a single covalent chemical bond or a divalent linking group; and z=2 when Y is a trivalent linking group on a surface of the electronic device substrate; (c) curing the layer of the curable compound to form an underlayer; (d) coating a layer of a photoresist on the underlayer; (e) exposing the photoresist layer to actinic radiation through a mask; (f) developing the exposed photoresist layer to form a resist pattern; and (g) transferring the pattern to the underlayer to expose portions of the electronic device substrate.

Description

EXAMPLE 1

[0036] 1,3,5-Tribromobenzene (2.36 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 20 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70 C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dioxane (14 g), and the solution was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction mixture was stirred for overnight at 70 C. under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was purified by column chromatography to give 1,3,5-tris((4-acetoxyphenyl)ethynyl)benzene (Compound I1) as a light yellow solid, 3.5 g (84% yield). The reaction is shown in the following reaction scheme.

##STR00013##

EXAMPLE 2

[0037] 1,3,5-Tribromobenzene (2.36 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 20 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70 C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dioxane (14 g), and the solution was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction mixture was stirred for overnight at 70 C. under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was purified by column chromatography to give a light yellow solid. This obtained solid was then dissolved in THF (35 g) under nitrogen. Lithium hydroxide monohydrate (0.94 g) and water (8 g) were added, and the reaction mixture was stirred at 60 C. for 1 hr. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined, and washed with water. The solvent was removed under vacuum to obtain 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (Compound I2) as a light yellow solid, 2.6 g (81% yield). The reaction is shown in the following reaction scheme.

##STR00014##

EXAMPLE 3

[0038] 4-Iodophenyl acetate (24.75 g), cuprous iodide (0.17 g) and triethylamine (27.32 g) were added to 22.82 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.63 g) was added to the reaction mixture, and the mixture was heated to 70 C. A solution of 1,3,5-triethynylbenzene (4.5 g) in degassed 1,4-dioxane (20 g) was then slowly added to reaction mixture via syringe pump. After completion of addition, the reaction was stirred for overnight at 70 C. under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, and solvents were evaporated. The residue was diluted with ethyl acetate and filtered to remove the solid. The solution was evaporated, and the residue was purified by column chromatography to give a light yellow solid. This obtained solid was then dissolved in THF (38 g) under nitrogen. Lithium hydroxide monohydrate (3.81 g) and water (16 g) were added, and the mixture was stirred at 60 C. for 1 hr. The mixture was then cooled to room temperature, and the solvent was removed. The residue was diluted with ethyl acetate and water, and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined, and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to obtain 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (Compound I2) as a light yellow solid, 7.7 g (61% yield). The reaction is shown in the following reaction scheme.

##STR00015##

EXAMPLE 4

[0039] 1,3,5-Tribromobenzene (3.12 g), cuprous iodide (0.29 g) and triethylamine (4.55 g) were added to 22 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.70 g) was added to the reaction mixture, and the mixture was heated to 70 C. 1-ethynyl-4-methoxybenzene (5.28 g) was dissolved in degassed 1,4-dioxane (20 g), and the solution was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction mixture was stirred overnight at 70 C. under nitrogen. After reaction was completed, the mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was purified by column chromatography to give 1,3,5-tris((4-methoxyphenyl)ethynyl)benzene (Compound I3) as a light yellow solid, 4.0 g (85% yield). The reaction is shown in the following reaction scheme.

##STR00016##

EXAMPLE 5

[0040] 1,3,5-Tribromobenzene (3.12 g), cuprous iodide (0.29 g) and triethylamine (4.55 g) were added to 22 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.70 g) was added to the reaction mixture, and the mixture was heated to 70 C. 4-Ethynylaniline (4.68 g) was dissolved in degassed 1,4-dioxane (20 g), and the solution was then slowly added to the reaction mixture by way of an addition funnel. After completion of addition, the reaction mixture was stirred overnight at 70 C. under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was purified by column chromatography to give 1,3,5-tris((4-aminophenyl)ethynyl)benzene (Compound I4) as a yellow solid, 1.5 g (36% yield). The reaction is shown in the following reaction scheme.

##STR00017##

EXAMPLE 6

[0041] 1,3,5-Tribromobenzene (15.0 g) was added to 40.0 g of 1,4-dioxane at room temperature to yield a clear solution. Triethylamine (14.5 g) and cuprous iodide (0.91 g) were added to the reaction mixture. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (1.00 g) was added to the reaction mixture. Next, 22.9 g of 4-fluorophenylacetylene was slowly added to reaction mixture via an addition funnel. After completion of addition, the reaction was stirred for 24 hr. at 55 C. under nitrogen. The reaction mixture was filtered and solvents were evaporated. The residue was dissolved in heptanes and filtered through a silica plug. After filtration, the solvents were removed to yield 1,3,5-tris((4-fluorophenyl)ethynyl)benzene (Compound IS) as a light yellow solid (8.0 g) in 39% yield. The reaction is shown in the following reaction scheme.

##STR00018##

EXAMPLE 7

[0042] 5,5Oxybis(1,3-dibromobenzene) (3.61 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 20 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70 C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dioxane (17 g), and the solution was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction mixture was stirred overnight at 70 C. under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was purified by chromatography to give a light yellow solid. This obtained solid was then dissolved in THF (40 g) under nitrogen. Lithium hydroxide monohydrate (1.26 g) and water (10 g) were added, and the mixture was stirred at 60 C. for 1 hr. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined, and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to give 5,5-oxybis(1,3-di((4-hydroxyphenyl)ethynyl)benzene) (Compound 16) as a light yellow solid, 3.1 g (65% yield). The reaction is shown in the following reaction scheme.

##STR00019##

EXAMPLE 8

[0043] 9,9-Bis(6-(3,5-dibromophenoxy)naphthalen-2-yl)-9H-fluorene (6.85 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 25 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70 C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dioxane (22 g), and the solution was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction mixture was stirred overnight at 70 C. under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was purified by chromatography to give a light yellow solid. This obtained solid was then dissolved in THF (40 g) under nitrogen. Lithium hydroxide monohydrate (1.26 g) and water (10 g) were added, and the mixture was stirred at 60 C. for 1 hr. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined, and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to give 9,9-bis(6-(3,5-di((4-hydroxyphenyl)ethynyl)phenoxy)naphthalen-2-yl)-9H-fluorene (Compound 17) as a light yellow solid, 4.7 g (59% yield). The reaction is shown in the following reaction scheme.

##STR00020##

EXAMPLE 9

[0044] 1,3,5-Trisbromobenzene (2.83 g), cuprous iodide (0.17 g) and triethylamine (4.10 g) were added to 20 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.32 g) was added to the reaction mixture, and the mixture was heated to 70 C. 2-((6-Ethynylnaphthalen-2-yl)oxy)tetrahydro-2H-pyran (6.81 g) was dissolved in degassed 1,4-dioxane (13 g), and the solution was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction mixture was stirred overnight at 70 C. under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was purified by chromatography to give white solid. This obtained solid was then dispersed in MeOH (54 g) under nitrogen. 12N HCl (4.5 g) and water (54 g) were added, and the mixture was refluxed overnight at 60 C. The reaction mixture was then cooled to room temperature, and solvent was removed under vacuum. The residue was diluted with ethyl acetate, and the organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined, and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to give 1,3,5-tris((2-hydroxynaphthyl-6-ethynyl)benzene (Compound 18) as a white solid 1.1 g (21% yield). The reaction is shown in the following reaction scheme.

##STR00021##

[0045] Compound I2 (6.0 g) in 46 g anhydrous DMF was stirred at room temperature for 15 minutes. The mixture was heated to 30 C. and 10.34 g K.sub.2CO.sub.3 was then added. The reaction was then allowed to heat to 50 C. and 8.63 g propargyl bromide (80% in toluene) solution was added dropwise via additional funnel. The reaction mixture was heated at 50 C. for 24 hours. The reaction was then allowed to cool down to room temperature and was filtered to remove most of K.sub.2CO.sub.3. The organic was precipitated into 2 L water, stirred at room temperature for 0.5 h. The precipitated polymer was collected by filtration to give solid (17.8 g) after dried under vacuum at 35 C. for 1 day.

##STR00022##

COMPARATIVE EXAMPLE 1

[0046] 1,3,5-Tris(4-bromophenyl)benzene (4.05 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) were added to 20 g of 1,4-dioxane at room temperature. The reaction mixture was purged with nitrogen for 1 hr. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70 C. 4-Ethynylphenyl acetate (4.81 g) was dissolved in degassed 1,4-dioxane (14 g), and the solution was then slowly added to reaction mixture by way of an addition funnel. After completion of addition, the reaction mixture was stirred overnight at 70 C. under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered and solvents were evaporated. The residue was purified by chromatography to give a light yellow solid. This obtained solid was then dissolved in THF (35 g) under nitrogen. Lithium hydroxy monohydrate (0.94 g) and water (8 g) were added, and the mixture was stirred at 60 C. for 1 hr. The reaction mixture was then diluted with ethyl acetate and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and aqueous phase was extracted with ethyl acetate. The organic layers were combined, and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to give 1,3,5-tris((4-(4-hydroxyphenyl)ethynyl)phenyl)benzene (Comparative 1) as a light yellow solid, 2.2 g (44% yield). The reaction is shown in the following reaction scheme.

##STR00023##

EXAMPLE 10

[0047] Solubility was evaluated by mixing a compound of the invention with each of PGME and PGMEA at 5% solids. Those mixtures were visibly inspected as well as checked using a turbidity meter (Orbeco-Hellige Co). If the turbidity value was less than 1, the compound was rated soluble (S) and if the turbidity value was greater than 1, it was rated not soluble (NS). The results are reported in Table 1. As can be seen from these data, the compounds of the invention and the Comparative compound are all soluble in each of PGME and PGMEA.

TABLE-US-00001 TABLE 1 Solubility (5% solids) Entry No. Compound PGMEA PGME 1 I2 S S 2 I6 S S 3 I9 S S 4 Comparative 1 S S

EXAMPLE 11

[0048] Thermal stability of compounds of the invention was evaluated using a Thermal Gravimetric Analyzer (TGA) Q500 from TA-Instruments, under the following conditions: under N.sub.2, ramp at 10 C./min. to 700 C.; and under air, ramp at 10 C./min. to 700 C. The temperature at which the materials lost 5% of their weight (Td.sub.5%) are reported in Table 2.

TABLE-US-00002 TABLE 2 Td.sub.5% ( C.) Entry No. Compound Under N.sub.2 Under Air 1 I2 504 470 2 I6 503 469 3 I9 471 398 4 Comparative 1 526 492

EXAMPLE 12

[0049] Solvent strip resistance was measured as an indication of film crosslinking Compositions of compounds of the invention and of Comparative Compound 1 were prepared in a mixture of PGMEA and benzyl benzoate at 4.5% solids. Each composition was spin-coated on an 8 (200 mm) silicon wafer at a rate of 1500 rpm using ACT-8 Clean Track (Tokyo Electron Co.), and then baked at the temperature reported in Table 3 for 60 seconds to form a film. Initial film thickness was measured using an OptiProbe from Therma-Wave Co. Next, a commercial remover, OK73 (PGME/PGMEA=70/30), was applied to each of the films for 90 seconds followed by a post strip baking step at 105 C. for 60 seconds. The thickness of each film following post strip baking was again measured to determine the amount of film thickness lost. The difference in film thickness before and after contact with the remover is reported in Table 3 as the percentage of film thickness remaining. As can be seen from the data, films formed from the compounds of the invention retained greater than 99% of their thickness, whereas the film formed from Comparative Compound 1 retained only 12% film thickness (that is, it lost 88% of its thickness) after contact with the remover.

TABLE-US-00003 TABLE 3 Entry No. Compound % Film Remaining 1 I2 >99 (230 C.) 2 I6 >99 (230 C.) 3 I9 >99 (300 C.) 4 Comparative 1 12 (230 C.)

EXAMPLE 13

[0050] Compositions of compounds of the invention and of Comparative Compound 1 were prepared in a mixture of PGMEA and benzyl benzoate at 4.5% solids. Each composition was spin-coated on an 8 (200 mm) silicon wafer at a rate of 1500 rpm using ACT-8 Clean Track (Tokyo Electron Co.), and then baked at the temperatures identified in Table 4 for 60 seconds to form a cured film. Optical constants were measured by Vacuum Ultra-Violet Variable Angle Ellipsometer (VUV-VASE, from Woollam Co.) at 193 nm, and are reported in Table 4.

TABLE-US-00004 TABLE 4 Refractive Index/ Absorbance at 193 nm Entry No. Compound (Temperature) n k 1 I2 (240 C.) 1.41 0.25 2 I9 (300 C.) 1.49 0.50 3 Comparative 1 (300 C.) 1.42 0.63

EXAMPLE 14

[0051] Compounds of the invention were evaluated to determine their gap-filling properties. Gap fill templates were created at CNSE Nano-FAB (Albany, N.Y.). The template had SiO.sub.2 film thickness of 100 nm, and various pitch and patterns. The template coupons were baked at 150 C. for 60 seconds as a dehydration bake prior to coating the coupons with the present compositions. Each coating composition (4.5% solids in a mixture of PGMEA, benzyl benzoate and PolyFox PF656) was coated on a template coupon using an ACT-8 Clean Track (Tokyo Electron Co.) spin coater and a spin rate of 1500 rpm+/200 rpm. The target film thickness was 100 nm after curing, and the composition dilution was adjusted accordingly to give approximately the target film thickness after curing. The films were cured by placing the wafer on a hot plate at the temperature identified in Table 5 for 60 sec. Cross-section scanning electron microscope (SEM) images of the coated coupons were collected using a Hitachi S4800 SEM (from Hitachi High Technologies). Planarization quality of the films was obtained from the SEM images using Hitachi offline CD measurement software or CDM software by measuring the difference in thickness between dense trench and open area of the film (FT). Films having a FT<20 nm were considered to have Good planarization and films having a FT>20 nm were considered to have Poor planarization. Gap filling was evaluated by visually inspecting the SEM images to see if there were any voids or bubbles in the trench patterns. Films having no voids in the trench patterns were considered to have Good gap fill and films having voids in the trench patters were considered to have Poor gap fill. These results are reported in Table 5.

TABLE-US-00005 TABLE 5 Sample No. Compound (Temperature) Planarization Gap Fill 1 I2 (240 C.) Good Good 2 I6 (240 C.) Good Good 3 I8 (300 C.) Good Good 4 I9 (300 C.) Good Good 5 Comparative 1 (300 C.) Poor Good

EXAMPLE 15

[0052] Compositions of compounds of the invention and of Comparative Compound 1 were prepared in PGMEA at 4.5% solids. Each composition was spin-coated on an 8 (200 mm) silicon wafer at a rate of 1500 rpm using an ACT-8 Clean Track (Tokyo Electron Co.), and then baked at the temperatures reported in Table 6 for 60 sec. to form a cured film. Coating quality was evaluated by visually inspecting the film, and the results are reported in Table 6.

TABLE-US-00006 TABLE 6 Entry No. Compound (Temperature) Coating Quality 1 I2 (240 C.) Good 2 I9 (300 C.) Good 3 Comparative 1 (300 C.) Poor

EXAMPLE 16

[0053] Each underlayer solution (4.5% solids in a mixture of PGMEA and benzyl benzoate) was spin coated at 1500 rpm on 200 mm silicon wafers using an ACT-8 Clean Track with targeted film thickness of 100 nm after curing. A virgin silicon wafer was placed upside down on top of the coated wafer with three (2 mm) spacers on the edge. The wafer stack was baked at the temperatures identified in Table 7 for 60 sec. on a hot plate with the coated wafer at the bottom. The top wafer was inspected for haze (which indicates sublimation) and defect using SP2 defect tool (from KLA-Tencor Corporation) with 500 nm sensitivity. As can be seen from the data in Table 7, Comparative Compound 1 gives significantly higher defect count and defect density than does Compound I2 of the present invention.

TABLE-US-00007 TABLE 7 Sublimation Defect (Less spacer defects) Entry No. Compound (Temperature) Defect Count Defect Density 1 I2 (240 C.) <8 <0.03 2 Comparative 1 (300 C.) >91000 >325