Gap-filling method

Abstract

A method of manufacturing a semiconductor device comprising: providing a semiconductor device substrate having a relief image on a surface of the substrate, the relief image having a plurality of gaps to be filled; applying a coating composition to the relief image to provide a coating layer, wherein the coating composition comprises (i) a polyarylene oligomer comprising as polymerized units one or more first monomers having two or more cyclopentadienone moieties and one or more second monomers having an aromatic moiety and two or more alkynyl moieties; wherein the polyarylene oligomer has a M.sub.w of 1000 to 6000 Da, a PDI of 1 to 2, and a molar ratio of total first monomers to total second monomers of 1:>1; and (ii) one or more organic solvents; curing the coating layer to form a polyarylene film; patterning the polyarylene film; and transferring the pattern to the semiconductor device substrate.

Claims

1. A method comprising: (a) providing a semiconductor device substrate having a relief image on a surface of the substrate, the relief image having a plurality of gaps to be filled; (b) applying a coating composition to the relief image and filling the gaps to provide a coating layer, wherein the coating composition comprises (i) a polyarylene oligomer comprising as polymerized units one or more first monomers having two or more cyclopentadienone moieties and one or more second monomers having an aromatic moiety and two or more alkynyl moieties; wherein the polyarylene oligomer has a M.sub.w of 1000 to 6000 Da, a polydispersity index (PDI) of 1 to 2, and a molar ratio of total first monomers to total second monomers of 1:>1; and (ii) one or more organic solvents; (c) curing the coating layer to form a polyarylene film; (d) disposing a layer of an inorganic hardmask on the polyarylene film; (e) disposing a layer of a photoresist on the inorganic hardmask layer; (f) patterning the photoresist layer; (g) transferring the pattern from the photoresist layer to the polyarylene film; and (h) then transferring the pattern to the semiconductor device substrate.

2. The method of claim 1 wherein the polyarylene oligomer has a M.sub.w of 2000 to 3500 Da.

3. The method of claim 2 wherein the polyarylene oligomer has a PDI of 1.25 to 1.75.

4. The method of claim 1 wherein the polyarylene oligomer has a degree of polymerization of 2 to 3.75.

5. The method of claim 1 wherein the molar ratio of total first monomers to total second monomers is 1:1.01 to 1:1.5.

6. The method of claim 1 further comprising disposing a layer of an organic antireflectant between the hardmask layer and the photoresist layer.

7. The method of claim 1 wherein the polyarylene oligomer further comprises as polymerized units one or more end-capping monomers.

8. The method of claim 1 wherein at least one first monomer has the structure shown in formula (1) ##STR00009## wherein each R.sup.10 is independently chosen from H, C.sub.1-6-alkyl, and optionally substituted C.sub.5-20-aryl; and Ar.sup.3 is an aryl moiety having from 5 to 60 carbons.

9. The method of claim 1 wherein at least one second monomer has the structure shown in formula (5) ##STR00010## wherein each Ar.sup.1 and Ar.sup.2 is independently a C.sub.5-30-aryl moiety; each R is independently chosen from H, and optionally substituted C.sub.5-30-aryl; each R.sup.1 is independently chosen from C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, C.sub.1-10-hydroxyalkyl, C.sub.1-10-alkoxy, CN, and halo; each Y is independently a single covalent chemical bond or a divalent linking group chosen from —O—, —S—, —S(═O)—, —S(═O).sub.2—, —C(═O)—, —(C(R.sup.9).sub.2).sub.z—, C.sub.6-30-aryl, and (C(R.sup.9).sub.2).sub.z1—(C.sub.6-30-aryl)-(C(R.sup.9).sub.2).sub.z2—; each R.sup.9 is independently chosen from H, hydroxy, halo, C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, and C.sub.6-30-aryl; a1=0 to 4; each a2=0 to 4; b1=1 to 4; each b2=0 to 2; a1+each a2=0 to 6; b1+each b2=2 to 6; d=0 to 2; z=1 to 10; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10.

10. The method of claim 1 further comprising the step of removing the polyarylene film.

Description

EXAMPLE 1

(1) A mixture of 30.0 g of 3,3′-(oxydi-1,4-phenylene)bis(2,4,5-triphenylcyclopentadienone) (DPO-CPD), 18.1 g 1,3,5-tris(phenylethynyl)benzene (TRIS) and 102.2 g of GBL was heated at 185° C. for 14 hrs. The reaction was then allowed to cool to room temp and diluted with 21.5 g of GBL. The crude reaction mixture was added to 1.7 L of a 1:1 mixture of isopropyl alcohol (IPA)/PGME and stirred for 30 min. The solid was collected by vacuum filtration and washed with 1:1 mixture of IPA/PGME. To the solid was added 0.4 L of water and the slurry was heated to 50° C. and stirred at 50° C. for 30 min. The warm slurry was filtered by vacuum filtration. The wet cake was vacuum dried for 2 days at 70° C. providing 34.1 g of Oligomer 1 in 71% yield. Analysis of Oligomer 1 provided a M.sub.w of 3487 Da and a PDI of 1.42.

EXAMPLE 2

(2) A mixture of 30.0 g of DPO-CPD, 18.1 g TRIS and 102.2 g of GBL was heated at 200° C. for 6 hrs. The reaction was then allowed to cool to room temp and diluted with 21.5 g of GBL. The crude reaction mixture was added to 1.7 L of a 1:1 mixture of IPA/PGME and stirred for 30 min. The solid was collected by vacuum filtration and washed with 1:1 mixture of IPA/PGME. To the solid was added 0.4 L of water and the slurry was heated to 50° C. and stirred at 50° C. for 30 min. The warm slurry was filtered by vacuum filtration. The wet cake was vacuum dried for 2 days at 70° C. providing 34.1 g of Oligomer 2 in 71% yield. Analysis of Oligomer 2 provided a M.sub.w of 3490 Da and a PDI of 1.42.

EXAMPLE 3

(3) The procedure of Example 2 was repeated to provide Oligomers 3 to 11. The molar ratio of total first monomer to total second monomer (F/S Mole Ratio) for each oligomer charged into the reaction vessel is reported in Table 1. Oligomers 3 to 11 were analyzed by gel permeation chromatography (GPC) on an Agilent GPC instrument with a differential refractometer operated at 35° C. The SEC column set used in this study was composed of Shodex-KF805, Shodex-KF804, Shodex-KF803 and Shodex-KF802 in series. The chromatography was performed in uninhibited THF at flow rate of 1 mL/min using polystyrene narrow standards of 162 to 483,000 Da were used for calibration. The determined M.sub.w for each of Oligomers 3 to 11 is reported below in Table 1, and was used to calculate the polydispersity index (PDI) and the degree of polymerization (DP), each of which is reported in Table 1.

(4) TABLE-US-00001 TABLE 1 Oligomer No. M.sub.w (Da) PDI DP F/S Mole Ratio 3 2254 1.47 2.04 1:1.25 4 2506 1.51 2.27 1:1.25 5 3046 1.59 2.76 1:1.25 6 3224 1.63 2.92 1:1.25 7 3544 1.6 3.21 1:1.25 8 3904 1.68 3.54 1:1.25 9 2204 1.45 2.00 1:1.11 10 3174 1.66 2.88 1:1.1 11 3994 1.75 3.62 1:1.1

EXAMPLE 4

(5) Oligomer 5 (10 g) from Example 3 was charged to a 100 mL single neck round bottom flask equipped with a reflux condenser, thermocouple and nitrogen atmosphere; followed by GBL (20 g). The reaction was stirred and warmed to 145° C., at which point phenyl acetylene (1 g) was added as an end-capping monomer. The reaction was kept at 145° C. for a total of 12 hours, at which point the reaction became transparent. The end-capped oligomer was isolated by precipitating the reaction mixture into an excess (200 g) of methyl tert-butyl ether (MTBE) to yield 7 g of End-Capped Oligomer EC1, as illustrated in the following reaction scheme.

(6) ##STR00008##

EXAMPLE 5

(7) DPO-CPD (100 g 0.128 mol, 1 eq) and TRIS (60.43 g, 0.160 mol, 1.25 eq) were charged to a 1 L, three-neck round bottom flask, followed by GBL (374 g, 30% solids). The solution was stirred and heated to 185° C. within 30 minutes and heated for an additional 16 hours. The reaction was then cooled to 145° C., and phenylacetylene (17.8 g, 1.136 eq) was added. The reaction was heated at 145° C. for a total of 12 hours, and then cooled to 20° C. Isolation of the resulting end-capped oligomer was accomplished by precipitation of the reaction into a mixture of MTBE and heptanes (700 mL+300 mL) to provide 112 g of End-Capped Oligomer EC2.

EXAMPLE 6

(8) The procedure of Example 4 was repeated except that the phenyl acetylene was replaced with each of the following end-capping monomers to provide the End-Capped Oligomers reported in Table 2.

(9) TABLE-US-00002 TABLE 2 End-Capped End-Capping Monomer Oligomer No. Propiolic Acid EC3 1,4-Butynediol EC4 Acetylendicarboxylic acid EC5 Ethynyl Phenol EC6 1,3-Diethynyl benzene EC7 Ethynyl Phthalic anhydride EC8 Diphenylacetylene EC9 Diethynyl benzoic acid EC10 Norbomadiene EC11 2,4,6-tris(phenylethynyl)anisole EC12

COMPARATIVE EXAMPLE 1

(10) A mixture of DPO-CPD and TRIS in a mole ratio of 1:1.08 at a concentration of 30-40 wt % of solids in GBL heated to the target temperature of 200° C. until an M.sub.w of approximately 8800 Da was obtained (approximately 10-15 hours). The reactor was then cooled to 120° C. to stop further reaction. Cyclohexanone was added to dilute the polyarylene polymer to form a storage solution. 1 L of the storage solution was added to 10 L of isopropanol over 30 minutes. After the addition was complete, the solution was stirred for 1 hour, after which time the resulting precipitate was filtered, washed with 1 L of IPA twice, followed by air drying and then vacuum drying at 50° C. overnight to provide 327.3 g of Comparative Oligomer 1. Comparative Oligomer 1 was analyzed by MALDI-time of flight mass spectrometry and GPC according to Example 4 and was found to have a Mw of ca. 7700, a PDI of 2.04, and a DP of 6.97. Comparative Oligomer 1 corresponds to the polyphenylene used in SiLK™ D, a commercially available product from The Dow Chemical Company.

COMPARATIVE EXAMPLE 2

(11) The procedure of Example 2 was repeated except that the ratio of DPO-CPD to TRIS was 1:0.88. The resulting Comparative Oligomer 2. Comparative Oligomer 2 was analyzed by MALDI-time of flight mass spectrometry and GPC according to Example 4 and was found to have a Mw of 3300, a PDI of 1.4, and a DP of 2.99.

EXAMPLE 7

(12) Formulations were prepared by dissolving each of Oligomers 3 to 1 and Comparative Oligomers 1 and 2 in a mixture of PGMEA and benzyl benzoate at approximately 4 wt % solids to provide Formulations 3 to 11 and Comparative Formulations 1 and 2, respectively. Similarly, Formulation 12 was prepared using End-Capped Oligomer EC1. Each obtained formulation was filtered through a 0.2 μm poly(tetrafluoroethylene) (PTFE) syringe filter before use.

EXAMPLE 8

(13) The formulation samples from Example 7 were mixed with solvents commonly used in semiconductor industry indicated in Table 3, and their compatibility was evaluated by mixing the samples and the solvent at 1:10 weight ratio. Turbidity of the resulting mixture was measured by a Turbidity meter from Orbeco-Hellige Co. Turbidity sensors measure suspended material in a liquid, typically by measuring the amount of light transmitted through the liquid. A higher turbidity value indicates a higher amount of material suspended in the liquid. Samples having a turbidity value of less than 1 in PGMEA/PGME (30/70 w/w) were considered to pass. Samples having a turbidity value of less than 25 in PGME were considered to pass. Table 3 shows the result of these turbidity determinations. Formulation samples of the invention showed good compatibility with various conventional clean room track solvents whereas the comparative formulation sample showed limited compatibility.

(14) TABLE-US-00003 TABLE 3 PGMEA/PGME Formulation 30/70 w/w PGME Ethyl Lactate 3 0.09 0.07 — 4 0.08 0.04 — 5 0.08 0.05 0.19 6 0.06 0.15 — 7 0.07 0.39 — 8 0.09 11 — 9 0.08 0.04 — 10 0.06 0.07 — 11 0.06 5.34 — 12 0.11 — — Comparative 1 3.5 234 >100 Comparative 2 0.08 7.02 —

EXAMPLE 9

(15) Thermal stability of cured films of certain oligomers of Example 3 were evaluated via thermogravimetric analysis (TGA) on a Q500 Thermal Gravimetric Analyzer from TA-Instruments. Films were cured at 170° C. for 60 seconds and 350° C. for 60 seconds in air. Cured films were prepared on bare silicon wafers and scraped off the wafer for thermogravimetric analysis. A sample of each cured film was analyzed to determine the temperature at which 5 wt % of the film was lost due to decomposition (T.sub.d(5%)) using the following conditions: under nitrogen atmosphere, ramp at 10° C./min to 150° C., isothermal hold at 150° C. for 10 min., followed by ramp at 10° C./min to 700° C. The T.sub.d(5%) for each film sample is reported in Table 4. Another sample of each cured film was also analyzed by thermogravimetric analysis to determine the percentage weight loss during a one hour isothermal hold at 450° C. using the following conditions: under nitrogen atmosphere, equilibrate at 35° C., isothermal hold for 5 min, ramp 100° C./minute to 450° C., followed by isothermal hold for 60 min at 450° C. The percentage weight loss of each film sample at 450° C. for 1 hour is reported in Table 4.

(16) TABLE-US-00004 TABLE 4 Film Formed From Oligomer 450° C. Weight Formulation No. T.sub.d(5%) (° C.) Loss (%) 3 3 499 3.8 4 4 499 3.9 5 5 516 3.0 6 6 511 3.5 7 7 517 3.3 8 8 500 2.8 9 9 509 3.1 11 11 496 3.4 12 EC1 530 2.2 Comparative 1 Comparative 1 480 4.1 Comparative 2 Comparative 2 475 4.7

(17) As can be seen from the data in Table 4, films formed from the oligomers of the invention show both an improved (lower) weight loss upon 1 hour heating at 450° C. and a higher decomposition temperature (T.sub.d(5%)) than the films formed from the comparative oligomers.