Coating compositions for use with an overcoated photoresist

Abstract

Organic coating composition are provided including antireflective coating compositions that can reduce reflection of exposing radiation from a substrate back into an overcoated photoresist layer and/or function as a planarizing or via-fill layer. Preferred organic coating compositions of the invention comprise one or more resins that can harden upon thermal treatment without generation of a cleavage product. Particularly preferred organic coating compositions of the invention comprise one or more components that comprise anhydride and hydroxy moieties.

Claims

1. A coated substrate comprising: an organic coating composition layer comprising 1) a first resin that comprises anhydride group and 2) a second resin that is distinct from the first resin and comprises hydroxyl groups, wherein the first and second resins are acrylate resins; a photoresist composition layer above the organic coating composition layer.

2. A substrate of claim 1 wherein the organic coating composition is free of an amine-containing crosslinker component and an epoxy crosslinker component.

3. A substrate of claim 1 wherein the organic coating composition is free of an amine-containing crosslinker component.

4. A substrate of claim 1 wherein the organic coating composition is free of an epoxy crosslinker component.

5. A substrate of claim 1 wherein the first resin or second resin comprises one or more phenyl groups.

6. A substrate of claim 1 wherein the organic coating composition layer is at least essentially free of an acid or acid generator compound.

7. A substrate of claim 1 wherein the photoresist composition layer comprises one or more resin with photoacid-labile groups and is substantially free of aromatic groups.

8. A substrate of claim 1 wherein the organic coating composition is an antireflective coating composition.

9. An antireflective composition for use with an overcoated photoresist layer, the antireflective coating composition comprising 1) a first resin that comprises anhydride group and 2) a second resin that is distinct from the first resin and comprises hydroxyl groups, wherein the first and second resins are acrylate.

10. An antireflective coating composition of claim 9 wherein the antireflective composition is free of an amine-containing crosslinker component and an epoxy crosslinker component.

11. An antireflective coating composition of claim 9 wherein the antireflective composition is free of an amine-containing crosslinker component.

12. An antireflective composition of claim 9 wherein the antireflective composition is free of an epoxy crosslinker component.

13. An antireflective composition of claim 9 wherein the first resin or second resin comprises one or more phenyl groups.

14. An antireflective composition of claim 9 wherein the antireflective composition is at least essentially free of an acid or acid generator compound.

15. A coating composition, comprising 1) a first resin that comprises anhydride group and 2) a second resin that is distinct from the first resin and comprises hydroxyl groups, wherein the first and second resins are acrylate resins.

Description

EXAMPLES 1-10RESIN SYNTHESES

(1) General Procedures for Anhydride-Polymer Synthesis as Employed in Examples 1-10

(2) The reaction set up consisted of a three-neck, round-bottom flask of appropriate size containing a magnetic stir bar, and fitted with a temperature probe, dropping funnel, water-cooled condenser, dispense line attached to a syringe fitted to a syringe pump, and a nitrogen inlet (blanket). The temperature was controlled using an oil bath in tandem with a hotplate/stirplate. Initially charged to the flask was a monomer and solvent. To the dropping funnel was added the initiator solution. A feed solution containing monomers and solvent was placed in the syringe and affixed to the syringe pump. The mixture in the flask was heated to approximately 70 C. before adding the initiator solution. The monomer solution in the syringe was then delivered to the reaction mixture at a continuous rate over a period of 3-3.5 hours. When the addition was complete, the reaction mixture was allowed to continue stirring at 70 C. for an additional 30 minutes. The reaction was then thermally quenched by removing the heat source, diluting with solvent, and allowing the mixture to cool to room temperature.

(3) GPC was determined relative to polystyrene standards with RI detection (495 dalton cutoff) and THF as elution solvent. Some polymers in the examples below were further characterized for either optical density (OD). The polymers were spin-coated from solution onto both silicon and quartz wafers. The thickness of the films on silicon was measured. The absorptivity of the films on quartz was determined by UV spectrophotometry. The absorptivity was measured against a blank quartz wafer. From the thickness and absorptivity measurements, the OD was calculated at 13 nm.

(4) Monomers:

(5) 3,4-Dihydro-2H-pyran (DHP)

(6) Maleic Anhydride (MA)

(7) 2-Hydroxyethyl Methacrylate (HEMA)

(8) t-Butyl Methacrylate (tBMA)

(9) 3,5-Bis(hexafluoro-2-hydroxy-2-propyl)cyclohexyl Methacrylate (HFACHM)

(10) Pentafluoroethyl Acrylate (PFA)

(11) Methyl Methacrylate (MMA)

(12) Styrene

(13) Benzyl Methacrylate (BMA)

(14) Initiators:

(15) V-601

(16) Vazo-67

(17) Solvents:

(18) Tetrahydrofuran (THF)

(19) Isopropanol (IPA)

(20) Methyl, 2-Hydroxyisobutyrate (HBM)

(21) In the following Examples 1-10, the above anhydride resin synthesis procedure was employed with reagents as specified in the particular example. The above-listed reagents were employed as designated with the specified abbreviations. The molar ratios of the repeat units of the produced resin is specified in the Example hearing, thus in Example, the produced resin 35/35/30 DHP/MA/HEMA had 35 mole percent of polymerized 3,4-dihydro-2H-pyran, 35 mole percent maleic anhydride and 30 mole percent 2-hydroxyethyl methacrylate.

EXAMPLE 135/35/30 DHP/MA/HEMA

(22) Initial contents to reaction flask: DHP 16.2 g (193 mmol), and THF 31.7 g

(23) To dropping funnel: V-601 2.53 g, and THF 3.71 g

(24) Added from syringe: MA 18.9 g (193 mmol), HEMA 21.5 g (165 mmol), and THE 22 g Diluent: THF 66 g

(25) Following the reaction, the solution was precipitated into IPA, washed with IPA, filtered, air-dried, and then dried in vacuo at 40 C overnight to yield 38 g (67%) of a dry powder.

(26) Mw=18,817, Mn=5347

EXAMPLE 245/50/5 MA/HEMA/TBMA

(27) Initial contents to reaction flask: MA 23.7 g (242 mmol), and HBM 44 g

(28) To dropping funnel: Vazo-67 2.6 g, and HBM 4.8 g

(29) Added from syringe: HEMA 34.9 g (268 mmol), tBMA 3.81 g (26.8 mmol), and HBM 46 g Diluent: HBM 490 g

(30) Mw=27,711, Mn=5567

EXAMPLE 345/50/5 MA/HEMA/TBMA

(31) Initial contents to the reaction flask: MA 23.7 g (242 mmol), and HIM 132 g

(32) To dropping funnel: Vazo-67 2.6 g, and HBM 14.5 g

(33) Added from syringe: HEMA 34.9 g (268 mmol), tBMA 3.81 (26.8 mmol), and HBM 48.5 g Diluent: HBM 390 g

(34) Mw=19,822, Mn=7992

EXAMPLE 450/50 MA/HFACHM

(35) Initial contents to the reaction flask: MA 4.1 g (42 mmol), and HBM 23 g

(36) To dropping funnel: Vazo-67 1.0 g, and HBM 6 g

(37) Added from syringe: HFACHM 20.9 g (42 mmol), and HBM 49 g Diluent: HBM 156 g

(38) Mw=36,741, Mn=12,469

EXAMPLE 550/30/20 MA/PFA/HEMA

(39) Initial contents to reaction flask: MA 11.2 g (114 mmol), and HBM 62.5 g

(40) To dropping funnel: Vazo-67 1.3 g, and HBM 7.3 g

(41) Added from syringe: PFA 14.0 g (69 mmol), HEMA 6.0 g (46 mmol), and HBM 27.7 g Diluent: HBM 182 g

(42) Mw=23,877, Mn=8322

EXAMPLE 645/30/25 MA/MMA/HEMA

(43) Initial contents to reaction flask: MA 25.6 g (261 mmol), and HBM 144 g

(44) To dropping funnel: Vazo-67 2.6 g, and HBM 14.5 g

(45) Added from syringe: HEMA 19.0 g (146 mmol), MMA 17.6 g (176 mmol), and HBM 36.5 g Diluent: HBM 390 g

(46) Mw=33,843, Mn=13,973

EXAMPLE 745/45/10 MA/MMA/HEMA

(47) Initial contents to reaction flask: MA 26.95 g (275 mmol), and HBM (150 g)

(48) To the dropping funnel: Vazo-67 2.6 g, and HBM 14.5 g

(49) Added from syringe: HEMA 7.95 g (61 mmol), MMA 27.5 g (275 mmol), and HBM 30.5 g Diluent: HBM 390 g

(50) Mw=33,588, Mn=13,893

EXAMPLE 820/35/45 Styrene/HEMA/MA

(51) Initial contents to reaction flask: MA 24.9 g (254 mmol), and HBM 141 g

(52) To the dropping funnel: Vazo-67 2.6 g, and HBM 15 g

(53) Added from syringe: HEMA 25.7 g (198 mmol), styrene 11.8 g (113 mmol), and HBM 39 g Diluent: HBM 390 g

(54) Mw=46,623, Mn=14,479, OD=8.51 (193 nm)

EXAMPLE 910/45/45 Styrene/HEMA/MA

(55) Initial contents to reaction flask: MA 24.3 g (248 mmol), and HBM 138.5 g

(56) To the dropping funnel: Vazo-67 2.6 g, and HBM 14.5 g

(57) Added from syringe: HEMA 32.3 g (248 mmol), styrene 5.7 g (55 mmol), and HBM 42 g Diluent: HBM 390 g

(58) Mw=34,778, Mn=12,993, OD=4.96 (193 nm)

EXAMPLE 1045/30/25 MA/HEMA/BMA

(59) Initial contents to reaction flask: MA 21.5 g (219 mmol), and HBM 125 g

(60) To dropping funnel: Vazo-67 3 g, and HBM 15 g

(61) Added from syringe: HEMA 19.0 g (146 mmol), BMA 21.5 g (122 mmol), and HBM 58 g Diluent: HBM 390 g

EXAMPLES 11-22 (Polymer Solutions)

(62) The examples in the below Tables 1 and 2 contain only polymer and HBM solvent. No other additives were used. Examples 11-15 contain only one polymer as indicated in Table 1. For Examples 16-22, three unique polymers are blended at the amounts indicated in Table 2, and are as follows:

(63) MA polymer=45/45/10 MA/MMA/HEMA (Mw=33,588)

(64) Polyester=Poly(1,4-dimethyl terephthalate-co-1,3,5-tris(2-hydroxyethyl)cyanuric acid (Mw-3000)

(65) Acrylate=40/60 HEMA/MMA (Mw=11,257)

(66) General Procedures for Coating Wafers

(67) For all wafers (silicon or quartz) spin-coated with the formulated samples, the spin time was 30 s, at 2000 rpm. Then the wafers were baked on a hotplate for 60 s at the temperature indicated in the tables below. The thickness of the films on silicon wafers was measured by ellipsometry (nanospeck).

(68) General Procedures for Measuring Solvent Resistance

(69) Each sample solution tested for solvent resistance was spin-coated onto a silicon wafer. The thickness of the wafer was measured using ellipsometry (nanospeck). HBM poured over the surface of the wafer and allowed to sit for 60 seconds. The wafer was then spun dry at 4000 rpm for 60 seconds and the thickness was measured again.

(70) TABLE-US-00001 TABLE 1 Change in Film Thickness Following Thermal Cure and Solvent Strip Example Polymer Mw 90 C. 115 C. 150 C. 180 C. 215 C. 11 45/50/5 27,711 7.4% 0.1% 1.2% 0% 0.1% MA/HEMA/tBMA 12 45/50/5 19,822 1.9% 0% 0.3% MA/HEMA/tBMA 13 35/35/30 23,151 .sup.0% DHP/MA/HEMA 14 20/35/45 46,623 0.2% Styrene/HEMA/MA 15 10/45/45 37,778 0.3% Styrene/HEMA/MA

(71) TABLE-US-00002 TABLE 2 Film Thickness Remaining After Thermal Cure and Solvent Strip MA Example Polymer Polyester Acrylate 120 C. 150 C. 180 C. 210 C. 240 C. 16 25 75 0.4% .sup.0% 3.2% 1.6% 2.1% 17 50 50 2.7% 3.0% 0.8% 78.9% 97.6% 18 75 25 0.1% 4.9% 12.7% 86.4% 96.4% 19 25 75 1.5% 3.3% 28.6% 40.1% 48.2% 20 50 50 4.1% 8.4% 50.7% 67.7% 77.8% 21 75 25 35.6% 71.8% 87.4% 91.1% 94.0% 22 100 68.9% 88.2% 95.0% 94.6% 95.2%

EXAMPLES 22-25 (Additional Coating Composition Processing)

(72) Examples 22-25 in Table 3 below demonstrate polymer insolubility to a typical resist solvent and to a developer after a thermal treatment. Poly(styrene-co-maleic anhydride), cumene terminated with a typical Mn of about 1,600 and poly(styrene-co-allyl alcohol) with a typical Mn of about 1,200 (both purchased from Aldrich Chemical Company) were co-dissolved in propylene glycol monomethylether acetate to form several 10 weight percent solutions containing different amounts of each polymer. The solutions were filtered through a 0.2 m filter and each spin coated on a set of two six inch wafers using a DNS track at 3000 rpm. The coated wafers were then heated for 60 seconds to the indicated temperature using a hot plate to induce cross-linking. One of the wafer of each set was covered with a puddle of ethyl lactate, EL, for 60 seconds and then spun dry. The second wafer was immersed in a bath of 0.26N tetramentylammonium hydroxide, TMAH, solution for 60 seconds followed by a water rinse and a nitrogen blow dry. Film thickness (FT) was measured after the bake and after the solvent or developer exposure using a Thermowave instrument.

(73) TABLE-US-00003 TABLE 3 % Styrene- co-allyl Bake Initial EL, TMAH, % Loss % Loss Examples alcohol C. FT 60 sec. 60 sec to EL to TMAH Example 22 50 200 2117 2097 1 200 2126 2129 0.13 Example 23 25 200 2132 2127 0.22 200 2135 2139 0.2 Example 24 200 2182 2178 0.2 20 200 2179 2181 0.1 DPH-MA- HEMA Example 25 225 8278 8236 0.5 100% 225 8365 8453 1.05

EXAMPLE 26LITHOGRAPHIC PROCESSING

(74) This example shows use of an underlying coating composition of the invention as an underlayer/anti reflective layer to a 193 nm resist.

(75) Process Conditions

(76) 1) Underlayer: 215 nm coating layer of Example 26 cured at 200 C./60 seconds on a vacuum hotplate;

(77) 2) Photoresist: 260 nm coating layer of an acrylate-based 193 nm photoresist soft-baked at 120 C./60 seconds on a vacuum hotplate;

(78) 3) Exposure: the applied photoresist layer was exposed to patterned 193 nm radiation;

(79) 4) Post-Exposure Bake: 120 C./60 seconds;

(80) 5) Development: the latent image was developed with 0.26N aqueous alkaline developer to provide a photoresist relief image.