WO2007094849A2

WO2007094849A2 - Antireflective coating material

Info

Publication number: WO2007094849A2
Application number: PCT/US2006/046811
Authority: WO
Inventors: Peng-Fei Fu; Eric Scott Moyer
Original assignee: Dow Corning Corporation
Priority date: 2006-02-13
Filing date: 2006-12-07
Publication date: 2007-08-23
Also published as: TW200731015A; WO2007094849A3

Abstract

Silsesquioxane resins useful in forming the antireflective coating having the formula (PhSiO(3-x)/2(OH)x)mHSiO(3-x)/2(OH)x)n(MeSiO(3-x)/2(OH)x)p(RSiO(3-x)/2(OH)x)q where Ph is a phenyl group, Me is a methyl group, R is a polyethylene oxide group, x has a value of 0, 1 or 2; m has a value of 0.01 to 0.99, n has a value of 0.01 to 0.99, p has a value of 0.01 to 0.99, q has a value of 0.01 to 0.50 and m + n + p + q ≈ l.

Description

ANTIREFLECTIVE COATING MATERIAL

CROSS-REFERENCE TO RELATED APPLICATIONS [0001] None. BACKGROUND OF THE INVENTION

[0002] With the continuing demand for smaller feature sizes in the semiconductor industry, 193 nm optical lithography has emerged very recently as the technology to produce devices with sub- 100 nm. The use of shorter wavelength of light requires the bottom antireflective coating (BARC) to reduce the reflection on substrate and dampen the photoresist swing cure by absorbing light that has passed through the photoresist. Commercially available antireflective coatings consist of both organic and inorganic based materials. Typically, the inorganic ARC, which exhibits good etch resistance, is CVD based and is subject to all the integration disadvantage of extreme topography; on the other hand, the organic ARC materials are applied by spin-on process and have excellent fill and planarization properties, but suffer from poor etch selectivity to organic photoresists. As a result, a material that offers the combined advantages of organic and inorganic ARC is highly desired.

BRIEF SUMMARY OF THE INVENTION [0003] This invention pertains to silsesquioxane resins that exhibit antireflective coating properties for 193 nm light. The silsesquioxane resins of this invention contain a polyethylene oxide silsesquioxane unit on the resin. The presence of the polyethylene oxide silsesquioxane unit result in a resin that easier to produce, and also form excellent spin-on films that exhibit lower water contact angles. Additionally the flms have excellent propylene glycol monomethyl ethyl acetate (PGMEA) and tetramethylammonium hydroxide (TMAH) resistance when produced by curing the resin at 250⁰C.

DETAILED DESCRIPTION OF THE INVENTION

[0004] In particular this invention pertains to a method of forming an antireflective coating on an electronic device comprising (A) applying to an electronic device an ARC composition comprising (i) a silsesquioxane resin having the formula (PhSiOo^^COHWmHSiOo-xyiCO^^nCMeSiO^-x_j^COH^_pCRSiOo^^CO^^_q where Ph is a phenyl group, Me is a methyl group, R is a polyethylene oxide group, x has a value of 0, 1 or 2; m has a value of 0.01 to 0.99, n has a value of 0.01 to 0.99, p has a value of 0.01 to 0.99, q has a value of 0.01 to 0.50 and m + n + p + q « 1; and

(ii) a solvent; and

(B) removing the solvent and curing the silsesquioxane resin to form an antireflective coating on the electronic device.

[0005] The silsesquioxane resins (i) useful in forming the antireflective coating have the formula

(PhSiO₍₃._x)/2(OH)_x)_mHSiO₍₃._x)/2(OH)_x)_n(MeSiO₍₃._x)/2(OH)_x)_p(RSiO₍₃._x)/2(OH)_x)_q where Ph is a phenyl group, Me is a methyl group, R is a polyethylene oxide group, x has a value of 0, 1 or 2; m has a value of 0.01 to 0.99, n has a value of 0.01 to 0.99, p has a value of 0.01 to 0.99, q has a value of 0.01 to 0.50 and m + n + p + q « 1. Alternatively m has a value of 0.05 to 0.95, alternatively 0.10 to 0.50, n has a value of 0.05 to 0.95, alternatively 0.10 to 0.50, p has a value of 0.05 to 0.95, alternatively 0.10 to 0.70 and q has a value of 0.01 to 0.3, alternatively 0.05 to 0.20. [0006] R is a polyethylene oxide group. By polyethylene oxide group it is meant a group having at least one repeating unit of -(CH₂CH₂O)-. The polyethylene oxides useful herein may be exemplified by, but not limited to -(CH₂)₃-(OCH₂CH2)_t-OMe,

-(CH₂)₃-(0CH₂CH₂)r0C(O)Me, -(CH₂)₃-(OCH₂CH₂)_t-OH₅ where t has a number selected from 0 to 50.

[0007] The silsesquioxane resin may be essentially fully condensed or may be only partially condensed. When the silsesquioxane resin is partially condensed less than 40 mole % of the units in the silsesquioxane resin should contain Si-OH groups. Higher amounts of these units can result in instability in the resin and the formation of gels. Typically 6 to 38 mole % of the units in the silsesquioxane resin contain Si-OH groups.

[0008] The silsesquioxane resin has a weight average molecular weight (Mw) in the range of 500 to 400,000 and preferably in the range of 500 to 100,000, alternatively 10,000 to 30,000. [0009] Silsesquioxane resins useful herein may be exemplified by, but not limited to (PhSi0₃/2)θ.05-0.15(HSi0₃/2)o.l5-0.25(MeSϊθ3/2)o.55-0.65(RSiθ3/2)θ.075-0.15 where R is

3-(polyglycol methyl ether)propyl: -(CHi)₃-(OCH₂CH₂)_I-OMe.

[0010] The silsesquioxane resins may be produced by methods known in the art. For example, the silsesquioxane resins may be produced by the hydrolysis and condensation of a mixture of a phenyl trialkoxysilane, hydrogen trialkoxysilane, methyl trialkoxysilane and a PEO containing trialkoxysilane. Alternatively they may be produced by the hydrolysis and condensation of a phenyl trichlorosilane, hydrogen trichlorosilane, methyl trichlorosilane and a PEO containing trichlorosilane. Alternatively, the silsesquioxane resins may be produced by the

where n' has a value of 0.06 to 0.96, with a double bond capped polyether monomer in the presence of a hydrosilylation catalyst.

[0011] The silsesquioxane resin is typically produced in the presence of a solvent. Any suitable organic or silicone solvent that does not contain a functional group which may participate in the reaction may be used in producing the silsesquioxane resin. The solvent is generally used in an amount of 40 to 98 weight percent based on the total weight of solvent and silane reactants, alternatively 70 to 90 weight percent. The reaction may be carried out as a dual phase or single-phase system.

[0012] Useful organic solvents may be exemplified by, but not limited to, saturated aliphatics such as n-pentane, hexane, n-heptane, and isooctane; cycloaliphatics such as cyclopentane and cyclohexane; aromatics such as benzene, toluene, xylene, mesitylene; ethers such as tetrahydrofuran, dioxane, ethylene glycol dietheyl ether, ethylene glycol dimethyl ether; ketones such as methylisobutyl ketone (MIBK) and cyclohexanone; halogen substituted alkanes such as trichloroethane; halogenated aromatics such as bromobenzene and chlorobenzene; esters such as isobutyl isobutyrate and propyl propronate. Useful silicone solvents may be exemplified by, but not limited to cyclic siloxanes such as octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. A single solvent may be used or a mixture of solvents may be used.

[0013] The reaction to produce the silsesquioxane resin can be carried out at any temperature so long as it does not cause significant gellation or cause curing of the silsesquioxane resin. Typically the reaction is carried out at a temperature in the range of 5 ⁰C to 150 ?C, with ambient temperature suggested.

[0014] The time to form the silsesquioxane resin is dependent upon a number of factors such as the temperature, the type and amount of silane reactants, and the amount of catalyst, if present. Typically the reaction time is from several minutes to several hours. One skilled in the art will be able to readily determine the time necessary to complete the reaction. [00151 Following completion of the reaction the catalyst, if used, may be optionally removed. Methods for removing the catalyst are well know in the art and would include neutralization, stripping or water washing or combinations thereof. The catalyst may negatively impact the shelf life of the silicone resin especially when in solution thus its removal is suggested. [0016] In the process for making the silsesquioxane resin, after the reaction is complete, volatiles may be removed from the silsesquioxane resin solution under reduced pressure. Such volatiles include alcohol by-products, excess water, catalyst, hydrochloric acid (chlorosilane routes) and solvents. Methods for removing volatiles are known in the art and include, for example, distillation.

[0017] Following the reaction to produce the silsesquioxane resin a number of optional steps may be carried out to obtain the silsesquioxane resin in the desired form. For example, the silsesquioxane resin may be recovered in solid form by removing the solvent. The method of solvent removal is not critical and numerous methods are well known in the art (e.g. distillation under heat and/or vacuum). Once the silsesquioxane resin is recovered in a solid form, the resin can be optionally re-dissolved in the same or another solvent for a particular use. Alternatively, if a different solvent, other than the solvent used in the reaction, is desired for the final product, a solvent exchange may be done by adding a secondary solvent and removing the first solvent through distillation, for example. Additionally, the resin concentration in solvent can be adjusted by removing some of the solvent or adding additional amounts of solvent.

[0018] An ARC composition is produced by combining the silsesquioxane resin (i) with a solvent (ii). The ARC composition is then applied to an electronic device, the solvent is removed and the silsesquioxane resin is cured to produce the antireflective coating. [0019] Typically the electronic device is a semiconductor device, such as silicon-based devices and gallium arsenide-based devices intended for use in the manufacture of a semiconductor component- Typically, the device comprises at least one semiconductive layer and a plurality of other layers comprising various conductive, semiconductive, or insulating materials.

[0020] The solvent useful herein may be the same or different from the solvent used in the production of the silsesquioxane resin. Useful solvents (ii) include, but are not limited to, 1- methoxy-2-proρanol, propylene glycol monomethyl ethyl acetate (PGMEA) and cyclohexanone, among others. The ARC composition typically comprises from about 10% to about 99.9 wt% solvent based on the total weight of the ARC composition, alternatively 80 to 95 wt %. [0021] The ARC composition can further comprise a cure catalyst. Suitable cure catalysts include inorganic acids, photo acid generators and thermal acid generators. Cure catalysts may be exemplified by, but not limited to sulfuric acid (H₂SO₄), (4-ethylthiophenyl) methyl phenyl sulfonium triflate and 2-Naphthyl diphenylsulfonium triftate. Typically a cure catalyst is present in an amount of up to 1000 ppm, alternatively 500 ppm, based on the total weight of the ARC composition.

[0022] Specific methods for application of the ARC composition to the electronic device include, but are not limited to, spin-coating, dip-coating, spay-coating, flow-coating, screen- printing and others. The preferred method for application is spin coating. Typically, coating involves spinning the electronic device, at about 2000 RPM, and adding the ARC composition to the surface of the spinning electronic device.

[0023] The solvent is removed and the silsesquioxane resin is cured to form the anti- reflective coating on the electronic device. The solvent may be removed by known methods such as heating or during application by spinning. [0024] Curing generally comprises heating the coated electronic device to a sufficient temperature for a sufficient duration to lead to curing. For example, the coated electronic device can be heated at 8O⁰C to 450⁰C for 0.1 to 60 minutes, alternatively 150⁰C to 275°C for of 0.5 to 5 minutes, alternatively 200⁰C to 25O⁰C for 0.5 to 2 minutes. Any method of heating may be used during the curing step. For example, the coated electronic device may be placed in a quartz tube furnace, convection oven or allowed to stand on hot plates. [0025] To protect the silsesquioxane resin from reactions with oxygen or carbon during curing, the curing step can be performed under an inert atmosphere. Inert atmospheres useful herein include, but are not limited to nitrogen and argon. By "inert" it is meant that the environment contain less than 50 ppm and preferably less than 10 ppm of oxygen. The pressure at which the curing and removal steps are carried out is not critical. The curing step is typically carried out at atmospheric pressure although sub or super atmospheric pressures may work also.

[0026] Once cured, the electronic device comprising the anti-reflective coating can be used in further substrate processing steps, such as photolithography. When used in photolithography, a resist image is formed over the anti-reflective coating. The process for forming the resist image comprises (a) forming a film of a resist composition on top of the anti-reflective coating; (b) imagewise exposing the resist film to radiation to produce an exposed film; and (c) developing the exposed film to produce an image. The anti-reflective coatings on the electronic device are particularly useful with resist compositions that are imagewise exposed to ultraviolet radiation having a wavelength of 157 nm to 365 ran, alternatively ultraviolet radiation having a wavelength of 157 nm or 193 nm. Once an image has been produced in the resist film, then a pattern is etched in the anti-reflective coating. Known etching materials may be used to remove the anti-reflective coating. Additional steps or removing the resist film and remaining anti-reflective coating may be employed to produce a device having the desired architecture.

EXAMPLES

[0027] The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. AU percentages are in wt. %. Example 1

_TPh ~H _JVIe .1PEO

T 0.075 * 0.2Oi 0.62 T 0.105

168g of propylene glycol methyl ether acetate (PGMEA), 5.63 g of phenyltrichlorosilane, 32.43g of methyltrichlorosilane, 14.Og of 3-(polyglycol methyl ether) propyltrichlorosilane and 9.48g of trichlorosilane were loaded into a flask at 20⁰C using a water-circulating bath under a nitrogen atmosphere. In a separate flask, 28Og PGMEA and 14g of water were added and mixed. The water/PGMEA solution was then added to the flask containing the chlorosilanes over a period of 60 minutes. After the addition the reaction flask was allowed to body for one hour. The solution was transferred to a separation funnel and washed with DI water twice (2 x 100 g). The solution was then mixed with about 4Og of EtOH. The

EtOH/PGMEA resin solution was stripped to a 10 wt% PGMEA solution. The result solution was filtered through a 0.2 mm Teflon filter and bottled for testing. GPC results (vs. PS): Mw = 16, 100, Mw/Mn = 4.40; The solution was spin-coated on a 4" wafer, and the film was cured at 25O⁰C for 1 min. Film thickness = 1692 A. Water contact angle = 69.7°, surface energy = 37.3 dynes/cm². Wet removal rate in 1 min.: 100% by NE-89.

Example 2

T 0.10 1 O.2θT 0.60 TT 0.1 168g of propylene glycol methyl ether acetate (PGMEA), 7.4Og of phenyltrichlorosilane, 31.39g of methyltrichlorosilane, 13.5g of 3 -(poly glycol methyl ether) propyltrichlorosilane and 9.48g of trichlorosilane were loaded into a flask at 20 ⁰C using a water-circulating bath under a nitrogen atmosphere. In a separate flask, 28Og PGMEA and 14g of water were added and mixed. The water/PGMEA solution was then added to the flask containing the chlorosilanes over a period of 60 minutes. After the addition the reaction flask was allowed to body for one hour. The solution was transferred to a separation funnel and washed with DI water twice (2 x 100 g). The solution was then mixed with about 4Og of EtOH. The EtOH/PGMEA resin solution was stripped to a 10 wt% PGMEA solution. The result solution was filtered through a 0.2 mm Teflon filter and bottled for testing. GPC results (vs. PS): Mw = 10,400, Mw/Mn = 3.50; The solution was spin-coated on a 4" wafer, and the film was cured at 250 ° C for 1 min. Film thickness = 1546 A. Water contact angle = 71.0°, surface energy = 37.6 dynes/cm². Wet removal rate in 1 min.: 100% by NE-89.

Example 3

_Ph _™H ,JVIe JEO ^τ 0.25 * 0.2(>Γ 0.451 0.1

145 g of T^o.TS^O.ioT^OΛS (^{10% solid in} PGMEA) was mixed with 7.8 g of allyl mono- hydroxyl poly(ethylene glycol) (MW = 400 g/mol). The mixture was then circulated by a fluid pump through a column packed with activated

catalyst beads at 50°C for 48 hours. The solution was diluted with more PGMEA to a 10 wt% PGMEA solution, filtered through a 0.2 mm Teflon filter and bottled for testing. GPC results (vs. PS): Mw = 9,120,

Mw/Mn = 9.32; The solution was spin-coated on a 4" wafer, and the film was cured at

25O⁰C for 1 min. Film thickness = 1546 A. Water contact angle = 74.0°, surface energy =

38.9 dynes/cm . Wet removal rate in 1 min.: 100% by NE-89.

Film Coating and Characterization

The film coating on wafers was processed on a Karl Suss CT62 spin coater. The resin PGMEA solution was first filtered through a 0.2 micron TEFLON filter and then spin coated onto standard single side four inch polished low resistively wafers or double sided polished FTIR wafers (spin speed = 2000 rpm; acceleration speed = 5000, time = 20 seconds unless otherwise indicated). Films were cured at a temperature (200 to 250⁰C) for 60 seconds as indicated in the tables using a rapid thermal processing (RTP) oven with a nitrogen gas purge. The film thickness, refractive index and k value were determined using a J. A. Woollam ellipsometer. The thickness values recorded were the average of nine measurements. PGMEA resistance after cure was determined by measuring the film thickness change before and after PGMEA rinse. The wet removal rate was assessed with two commercial wet stripping solutions NE89 (available from ATMI) and CCl (available from ACT). Contact angle measurements were conducted using water and methylene iodide as liquids and the critical surface tension of wetting was calculated based on the Zisman approach. Results are summarized in Table 1. Table 1. Optical and Cure Properties

n k Mw Mw/Mn Th₅ A ΔTh, A ΔTh, A

Example 193 run 193nm vs. PS vs. PS 250⁰C, 1 min PGMEA TMAH

1 1.664 0.158 16100 4.4 1692 8 11

2 1.610 0.217 10400 3.5 1546 12 16

3 1.740 0.391 9120 9.3 2389 7 19

Claims

That which is claimed is:

1. A method of forming an antireflective coating on an electronic device comprising

(A) applying to an electronic device an ARC composition comprising (i) a silsesquioxane resin having the formula

(PhSiO₍₃._x)/2(OH)_x)_mHSiO₍₃._x)/2(OH)_x)_n(MeSiO₍₃._x)/2(OH)_x)p(RSiO₍₃._x)/2(OH)_x)_q where Ph is a phenyl group, Me is a methyl group, R is a polyethylene oxide group, x has a value of 0, 1 or 2; m has a value of 0.01 to 0.99, n has a value of 0.01 to 0.99, p has a value of 0.01 to 0.99, q has a value of 0.01 to 0.50 and m + n + p + q « 1; and (ii) a solvent; and

2. The method as claimed in claim 1 wherein m has a value of 0.01 to 0.50, n has a value of 0.01 to 0.80, p has a value of 0.01 to 0.80, and q has a value of 0.01 to 0.20.

3. The method as claimed in claim 1 wherein in the silsesquioxane resin less than 40 mole % of the units contain Si-OH groups.

4. The method as claimed in claim 1 wherein in the silsesquioxane resin 6 to 38 mol % of the units contain Si-OH groups.

5. The method as claimed in claim 1 wherein the solvent (ii) is propylene glycol methyl ether acetate.

6. The method as claimed in claim 1 wherein the ARC composition contains 80 to 95 wt% of solvent, based on the weight of the ARC composition.

7. The method as claimed in claim 1 wherein the ARC composition is applied by spin- coating.

8. The method as claimed in claim 1 wherein the silsesquioxane resin is cured by heating.

9. The method as claimed in claim 8 wherein the silsesquioxane resin is cured by heating at a temperature in the range of 15O⁰C to 275°C.

10. The method as claimed in claim 1 wherein the silsesquioxane resin is cured by heating at a temperature in the range of 200⁰C to 250⁰C.

11. The method as claimed in claim 1 wherein the silsesquioxane resin is cured by heating in an inert atmosphere.

12. A method of forming an antireflective coating on an electronic device comprising (A) applying to an electronic device an ARC composition comprising

(i)a silsesquioxane resin having the formula

where Ph is a phenyl group, Me is a methyl group, R is a polyethylene oxide group, x has a value of 0, 1 or 2; m has a value of 0.01 to 0.99, n has a value of 0.01 to 0.99, p has a value of 0.01 to 0.99, q has a value of 0.01 to 0.50 and m + n + p + q « l; and

(ii) a solvent; (B) removing the solvent and curing the silsesquioxane resin to form an antireflective coating on the electronic device; and (C) forming a resist image over the antireflective coating.

13. The method as claimed in claim 12 wherein the resist image is formed by

(a) forming a film of a resist composition on top of the anti-reflective coating;

(b) imagewise exposing the resist film to radiation to produce an exposed film;

(c) developing the exposed film to produce the image. ^•

14. A method of forming an antϊreflective coating on an electronic device comprising

(A) applying to an electronic device an ARC composition comprising

(i)a silsesquioxane resin having the formula

(PhSiO_(S-_X)Z₂(OH)_x)_Jn HSiO₍₃._x)^(OH)_x)_n(MeSiO₍3.χ>2(OH)_x)pCRSiO₍3._xy2(OH)_x)_q where Ph is a phenyl group, Me is a methyl group, R is a polyethylene oxide group, x has a value of 0, 1 or 2; m has a value of 0.01 to 0.99, n has a value of 0.01 to 0.99, p has a value of 0.01 to 0.99, q has a value of 0.01 to 0.50 and m + n + p + q « 1; and (ii) a solvent;

(B) removing the solvent and curing the silsesquioxane resin to form an antireflective coating on the electronic device;

(C) forming a resist image over the antireflective coating; and

(D) etching a pattern in the anti-reflective film.

15. A method of forming an antireflective coating on an electronic device comprising (A) applying to an electronic device an ARC composition comprising

(i)a silsesquioxane resin having the formula

where Ph is a phenyl group, Me is a methyl group, R is a polyethylene oxide group, x has a value of 0, 1 or 2; m has a value of 0.01 to 0.99, n has a value of 0.01 to 0.99, p has a value of 0.01 to 0.99, q has a value of 0.01 to 0.50 and m + n + p + q « 1 ; and (ii) a solvent; and

(C) forming a resist image over the antireflective coating; (D) etching a pattern in the anti-reflective film; and

(E) removing the resist image and the anti-reflective film.

16. An ARC composition comprising

(i) a silsesquioxane resin having the formula (PhSiO₍₃-χ_)/2(OH)_x)_mHSiO₍₃._x)/2(OH)_x)_n(MeSiO₍₃._x)/2(OH)_x)_p(RSiO₍₃._x)/2(OH)_x)_q where Ph is a phenyl group, Me is a methyl group, R is a polyethylene oxide group, x has a value of 0, 1 or 2; m has a value of 0.01 to 0.99, n has a value of 0.01 to 0.99, p has a value of 0.01 to 0.99, q has a value of 0.01 to 0.50 and m + n + p + q « 1 ; and

(ii) a solvent.

17. The composition as claimed in claim 16 wherein m has a value of 0.01 to 0.50, n has a value of 0.01 to 0.80, p has a value of 0.01 to 0.80, and q has a value of 0.01 to 0.20.

18. The composition as claimed in claim 16 wherein in the silsesquioxane resin less than 40 mole % of the units contains Si-OH groups.

19. The composition as claimed in claim 16 wherein in the silsesquioxane resin 6 to 38 mol % of the units contain Si-OH groups.

20. The composition as claimed in claim 16 wherein the solvent (ii) is propylene glycol methyl ether acetate.

21. The composition as claimed in claim 16 wherein the ARC composition contains 80 to 95 wt% of solvent, based on the weight of the ARC composition.

22. The composition as claimed in claim 16 wherein R is a polyethylene oxide group and the polyethylene oxide group is any organic substituent containing at least one ethylene oxide unit.

23. The composition as claimed in claim 16 wherein the polyethylene oxide group has the general formula: HOH₂MOCH₂CH₂X-OMe, -(CH₂)_S-(OCH₂CH₂VOC(O)Me, -(CH₂)_S-(OCH₂CH₂VOH where t is 0 to 50.